Nikolay Tsyrulin - Neutron Scattering Studies of Low-Dimensional Quantum Spin Systems

diss. eth no.
18845
Neutron Scattering Studies of Low-Dimensional
Quantum Spin Systems
A dissertation submitted to
ETH Z
URICH
for the degree of
Doctor of Science
presented by
NIKOLAY TSYRULIN
Dipl. Phys. MSU
born 19.11.1983
Russian citizen
accepted on the recommendation of
Prof. Dr. M. Troyer, examiner
Prof. Dr. J. Mesot, co-examiner
Dr. M. Kenzelmann, co-examiner
2010
ii
Contents
Abstract vii
Kurzfassung ix
1 Theoretical introduction and motivation 1
1.1 Quantum magnetism in two dimensions . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Ground state properties of S = 1/2 Heisenberg antiferromagnets . . . 2
1.1.2 Eects of applied eld on S = 1/2 Heisenberg antiferromagnets . . . . 6
1.2 Quantum phase transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.1 Bose-Einstein condensation of magnons in quasi-1D systems . . . . . 10
1.2.2 Quantum phase transitions in 2D square-lattice antiferromagnets . . 13
1.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.4 Structure of the thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2 Neutron scattering 19
2.1 Main properties of the neutron . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1.1 Neutron sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1.2 Energy and time scales . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2 Elastic neutron scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.1 Fermis Golden rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.2 Nuclear scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2.3 Magnetic scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.3 Neutron spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.1 Inelastic nuclear scattering . . . . . . . . . . . . . . . . . . . . . . . . 27
iv Contents
2.3.2 Inelastic magnetic scattering . . . . . . . . . . . . . . . . . . . . . . . 28
2.4 Experimental technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.4.1 Three-axis spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.4.2 The experimental resolution function . . . . . . . . . . . . . . . . . . 31
2.5 Sample environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.5.1 Split coil magnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.5.2 Dilution refrigerator . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3 2D S = 1/2 antiferromagnet on a square lattice Cu(pz)
2
(ClO
4
)
2
37
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2 Bulk properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2.1 Crystal structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2.2 Magnetic susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.2.3 Specic heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3 Neutron diraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3.1 Experimental details . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3.2 Magnetic order parameter . . . . . . . . . . . . . . . . . . . . . . . . 46
3.3.3 Ordered magnetic structure . . . . . . . . . . . . . . . . . . . . . . . 48
3.4 Neutron spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.4.1 Experimental details . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.4.2 Spin dynamics in zero eld . . . . . . . . . . . . . . . . . . . . . . . . 51
3.4.3 Spin dynamics in applied magnetic elds . . . . . . . . . . . . . . . . 58
3.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4 Magnetism in S = 1 quasi-1D antiferromagnet NiCl
2
4SC(NH
2
)
2
67
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.2 Experimental details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.3 Results and discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.3.1 Ordered magnetic structure . . . . . . . . . . . . . . . . . . . . . . . 72
4.3.2 Magnetic phase diagram . . . . . . . . . . . . . . . . . . . . . . . . . 76
Contents v
4.3.3 Bose-Einstein condensation of magnons . . . . . . . . . . . . . . . . . 79
4.3.4 Spin dynamics in the fully magnetized phase . . . . . . . . . . . . . . 83
4.3.5 Spin dynamics at the rst critical eld . . . . . . . . . . . . . . . . . 87
4.3.6 Spin dynamics deep in the antiferromagnetic phase . . . . . . . . . . 88
4.3.7 Spin dynamics in the antiferromagnetic phase with H ,| c . . . . . . . 95
4.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Outlook 99
Appendix A 101
Appendix B 105
Appendix C 109
Acknowledgments 125
Publications and conferences 127
Curriculum Vitae 129
vi Contents
Abstract
This thesis is devoted to experimental studies of magnetism in low dimensions. Being of great
fundamental interest, low dimensional magnets support strong quantum uctuations which
can result in novel quantum excitations and novel ground states. We used neutron scat-
tering technique to study two macroscopic quantum systems: (A) two-dimensional weakly-
frustrated S = 1/2 antiferromagnet on a square lattice, Cu(pz)
2
(ClO
4
)
2
, and (B) strongly
anisotropic quasi-one-dimensional S = 1 chain, NiCl
2
4SC(NH
2
)
2
.
(A) A comprehensive experimental study of the two-dimensional S = 1/2 square-lattice
antiferromagnet, Cu(pz)
2
(ClO
4
)
2
, was performed up to one third of the magnetic saturation
eld. The spin Hamiltonian of the system is determined precisely. Our experiments provide
evidence for the presence of a small antiferromagnetic next-nearest neighbor interactions
which enhances quantum uctuations associated with resonating valence bonds in the square-
lattice S = 1/2 antiferromagnet. We show that magnetic elds of the order of one third of
the saturation value lead to a qualitative change of the quantum uctuations that inverts the
zone-boundary dispersion.
(B) NiCl
2
4SC(NH
2
)
2
is a quasi-one-dimensional anisotropic S = 1 quantum magnet
which undergoes a eld-induced quantum phase transition from a quantum paramagnetic to
a three-dimensional antiferromagnetic state. This process can be treated theoretically as a
Bose-Einstein condensation of magnons. We directly observe the eld-induced closing of the
energy gap using inelastic neutron scattering. The phase diagram and the symmetry of the
antiferromagnetic order are determined, showing the order of the transverse spin components.
The study of the spin dynamics in the fully saturated ferromagnetic phases revealed nearest
neighbor exchange interactions. The study in the antiferromagnetic phase, on the other
hand, revealed additional spin interactions that are not present outside this phase, providing
viii Abstract
evidence of a coupling between magnetism and the crystal structure and the presence of
additional spin anisotropies in the material.
Kurzfassung
In dieser Arbeit wird eine experimentelle Studie uber Magnetismus in niedrigen Dimensio-
nen vorgestellt. Es besteht ein fundamentales Interesse an niedrig-dimensionierten Mag-
neten, da diese enorme Quantenuktuationen beg unstigen, was wiederum in neuartigen
Quantenanregungs- und Grundzust unden resultieren kann. Es wurden verschiedene Tech-
niken der Neutronenstreuung eingesetzt, um zwei makroskopische Quantensysteme zu studie-
ren: (A) ein zweidimensional, schwach-frustrierter S = 1/2 Antiferromagnet in einem Quadrat-
gitter, Cu(pz)
2
(ClO
4
)
2
, und (B) eine stark anisotrope quasi-eindimensionale S = 1 Kette,
NiCl
2
4SC(NH
2
)
2
.
(A) Eine umfassende experimentelle Studie wurde an dem System des zweidimensionalen
S = 1/2 Quadratgitter Antiferromagneten, Cu(pz)
2
(ClO
4
)
2
, durchgef uhrt, in magnetischen
Feldern von einer St arke bis zu einem Drittel des Sattigungswertes. Der Spin Hamiltonian
des Systems wurde prazise bestimmt. Unsere Experimente erbringen den Beweis der Existenz
einer kleinen antiferromagnetischen Wechselbeziehung zwischen nachsten Nachbarn, welche
Quantenuktuationen beg unstigt, die mit Resonanz-Valenz-Bindungen im Quadratgitter des
S = 1/2 Antiferromagneten in Verbindung stehen. Wir zeigen, dass magnetische Felder in der
Gr ossenordnung von einem Drittel des S attigungswertes zu einer qualitativen Ver anderung
der Quantenuktuationen f uhren, die die Zonengrenzen Dispersion umkehren.
(B) Das quasi-eindimensionale S = 1 Kettensystem ist in NiCl
2
4SC(NH
2
)
2
realisiert und
untergeht einer Feld-induzierten Quantenphasenumwandlung von einem quanten-paramagne-
tischen zu einem dreidimensionalen antiferromagnetischen Zustand. Dieser Prozess kann the-
oretisch als Bose-Einstein Verdichtung der Magnonen gesehen werden. Wir beobachten direkt
das Feld-induzierte Schliessen der Energiel ucke bei Verwendung von inelastischer Neutronen-
streuung. Das Phasendiagramm und die Symmetrie der antiferromagnetischen Ordnung wur-
x Kurzfassung
den untersucht und zeigen die Anordnung der querverlaufenden Spin Komponenten. Studien
der Spin-Dynamik in der vollig ges attigten ferromagnetischen Phase zeigen die Pr asenz von
n achste-Nachbarn Wechselwirkungen. Messungen in der Feld-induzierten antiferromagnetis-
chen Phase, auf der anderen Seite, zeigen die Pr asenz von Wechselwirkungen, die sonst nicht
da sind. Diese Messungen sind daher Indikationen f ur eine Kopplung von Magnetismus und
der Kristallstruktur sowie die Pr asenz von zus atzlichen Spin-Anisotropien in dieser Phase.
Chapter 1
Theoretical introduction and
motivation
1.1 Quantum magnetism in two dimensions
Low-dimensional magnets can have unusual ground states and spin correlations, especially
for small spin values such as S = 1/2. A prime historical example is the class of the
high-temperature superconducting cuprates whose undoped insulating phases consist of two-
dimensional (2D) antiferromagnetic planes of spins S = 1/2 [1]. Superconductivity emerges
upon doping of the 2D lattices. While anisotropic 2D antiferromagnets order at nite temper-
atures, isotropic 2D systems can adopt long range magnetic order only at zero temperature
[2]. But even then a ground state is not completely ordered due to the quantum uctuations
and, if present, geometrical frustrations.
Generally, the increase of the dimensionality from one to two reduces quantum uctua-
tions. For instance, antiferromagnetic chains with S = 1/2 do not order at zero temperature,
however 2D antiferromagnet (AF) on a square lattice possess semi-classical Neel order [1].
Magnetic order can be destroyed by geometrical frustrations, like in an AF on a triangular
lattice [3] or by competing interactions between neighboring and next-neighboring spins. Tun-
ing of competing interactions and quantum uctuations (for instance by external magnetic
eld) can move a system towards quantum criticality. Quantum uctuations are supported
by three-dimensional magnets as well [4], nevertheless their inuence and eects are typically
2 Theoretical introduction and motivation
Figure 1.1: Two bipartite lattices - square, honeycomb and two frustrated - triangular and
kagome are shown in (a), (b), (c) and (d), respectively.
much lower compared to the 2D case. In this section, we briey review the main character-
istics of the 2D S = 1/2 AF on four lattices - two bipartite (i.e. non-frustrated) square and
honeycomb and two frustrated, triangular and kagome (Fig 1.1).
1.1.1 Ground state properties of S = 1/2 Heisenberg antiferromag-
nets
Bipartite lattices
The existence of Neel order in Heisenberg AF (HAF) on a square lattice was proven for the
case of S > 1 [5, 6] and for the anisotropic Ising limit [7, 8]. However there is no strict proof
of the long-range order in case of S = 1/2 HAF. Starting with the work of Anderson [9], the
S = 1/2 HAF on a square lattice (Fig 1.1(a)) was studied for decades. Quantum uctuations
in the system lead to the renormalization of the order parameter by 60% compared to the
classical predictions. The Lieb-Mattis theorem [10] postulates that the quantum ground state
is a rotationally invariant singlet for nite bipartite lattices. Low-energy magnetic excitations
called magnons have a dispersion which can be calculated using spin-wave theory. Fig 1.2
shows the result of the rst-, second- and third-order spin-wave calculations for the S = 1/2
HAF on a square lattice. The excitation spectra of the semiclassically ordered HAF on a
nite square lattice have an energy gap between a singlet ground state and the rst excited
state. This gap vanishes for the Neel ground state in the thermodynamic limit leading to the
formation of the Goldstone mode. Consequently, a nite energy gap for a S = 1/2 HAF on a
square lattice at zero temperature can be the sign for spin anisotropies in the system or the
1.1 Quantum magnetism in two dimensions 3
Figure 1.2: The dispersion of the one-magnon excitation spectra along the high-symmetry
directions for the Heisenberg AF on a square lattice. The black circles represent the result of
series expansion calculations. The results of rst-, second and third-order spin-wave theory
are shown by blue dotted, red dashed and green solid lines, respectively. The gure is taken
from the publication of W. Zheng et al. [11].
result of a quantum spin liquid ground state that may arise from competing interactions.
Numerical studies of the 2D S = 1/2 HAF on a square lattice using quantum Monte
Carlo, exact diagonalization, coupled cluster as well as series expansion calculations reveal
a quantum renormalization of the one-magnon energy in the entire Brillouin zone. The
one-magnon dispersion along the high-symmetry directions of the Brillouin zone obtained
by series expansion calculations [11] is shown in Fig. 1.2. The main qualitative dierence
between the result of this numerical method and the high-order spin-wave theory is a magnon
dispersion along the antiferromagnetic zone boundary. This can be viewed as a pure quantum
eect, because spin-wave theory is based on the assumption that the ground state of S =
1/2 HAF is a classical Neel state. Numerical calculations also predict the existence of a
magnetic continuum at higher energies, near the minima of the zone-boundary dispersion
[11, 12, 13, 14, 15]. The zone boundary dispersion and a magnetic continuum in the excitation
spectra of the 2D S = 1/2 HAF on a square lattice can be a sign of the resonance valence bond
(RVB) ground state, as shown in Fig. 1.3(b). This state can be viewed as a superposition of
local singlets between spins on nearest sites [3].
Kobe and collaborators [16] proposed the ground state energy per bond of the classical
AF on bipartite lattices to be equal to E
classical
gs
/bond = S
2
. The ground state energy per
bond and the order parameter was calculated by various techniques. Quantum Monte Carlo
calculations [17, 18] give E
gs
/bond = 0.334719 and m = 0.3070. Here m is the sublattice
magnetization dened as
m =
1
N
i
S
z
i
, (1.1)
where N is the total number of spins and the case of m = 1 corresponds to a completely
ferromagnetic alignment of spins. The dierence between the calculated value and the clas-
sical expectation underlines the importance of quantum uctuations in 2D AF on bipartite
lattices.
The reduction of the coordination number, i.e. the number of nearest neighbors, strongly
aects the ground state properties of 2D spin systems. In order to illustrate this eect, we
give the example of the honeycomb lattice (Fig 1.1(b)), where every spin site has only three
nearest neighbors. Several techniques provide evidence that the ground state of this model is
semi-classical Neel order. Such results were obtained theoretically using the quantum Monte
Carlo simulations [19], the coupled-cluster, exact diagonalization of nite systems [20] and the
Schwinger-boson approach [21]. The ground state energy per bond and the order parameter
calculated by Quantum Monte Carlo [19] are equal to E
gs
/bond = 0.3630 and m = 0.235,
respectively. Those values are lower than it expected from classical approach and even lower
compare to the parameters of HAF on a square lattice. The reduction of magnetic order
parameter indicates enhanced quantum uctuations in a honeycomb lattice in comparison
with a square lattice due to the lowering of the coordination number.
Frustrated lattices.
In 2D spin systems the eect of quantum uctuations may be enhanced drastically by geo-
metrical frustrations. S = 1/2 HAF on the triangular lattice is strongly frustrated, however
the number of the nearest-neighbor spins is the highest for the considered 2D systems and
equal to six (Fig. 1.1(c)). Anderson and Fazekas [3, 22] proposed a quantum spin liquid
ground state for S = 1/2 AF on a triangular lattice. However, the signature of the Neel order
was later found using various numerical techniques, like the exact diagonalization of nite
system [23, 24] or quantum Monte Carlo [25]. The translational symmetry is broken due to
the angle of 120
between the spins in dierent sublattices in the case of the classical ground
state. The low-lying spin excitations in a triangular lattice can be described by spin-wave
theory. The ground state energy per bond and the sublattice magnetization calculated by
Capriotti et al [25] are equal to E
gs
/bond = 0.1819 and m = 0.205, respectively. This result
implies that quantum uctuations strongly aect the ground state. The results of quantum
Monte Carlo calculations scaled to the classical values are listed in Tab 1.1 for a range of
dierent lattices.
Lattice E
calc
0
/bond m/m
class
Square 0.3347 0.614
Honeycomb 0.3630 0.47
Triangle 0.1819 0.41
Kagome 0.2126 0
Table 1.1: The summarized data of quantum Monte Carlo calculations of the ground state
energy per bond and the magnetic order parameter. The order parameter (sublattice mag-
netization) is scaled to the classical prediction to give a feeling of amount of the quantum
uctuations in the systems. For kagome lattice presented results obtained by the coupled
cluster method.
After the discovery of the semi-classically ordered ground state in S = 1/2 HAF on
triangular lattice, the kagome
1
lattice (Fig. 1.2(d)) eventually became the rst candidate
for the investigations of a hidden order in 2D [26] or a possible quantum spin liquid state
[27, 28]. Exact diagonalization calculations proposed the quantum spin liquid as ground
state of the kagome lattice. Series expansions calculations performed by Singh and Huse
[29] showed that a valence bond crystal (VBC) with a 36 site unit cell is the ground state
of the S = 1/2 HAF on a kagome lattice (see Fig. 1.3(a)). VBC is characterized by the
formation of local singlets built by an even number of spins with weak correlations [30].
1
the name came from Japanese words me meaning the pattern of holes and kago - a basket
Figure 1.3: (a) Ground-state
ordering pattern for the kagome-
lattice Heisenberg model [29].
Dimers with strong and
weak bones are shown by
thick blue and thin black lines,
respectively. (b) Cartoon of the
RVB state on a square lattice.
However the experimental evidence for such a ground state
has not yet been found. Hiroi and co-workers [31] per-
formed experimental studies of a novel cuprate volborthite
compound Cu
3
V
2
O
7
(OH)
2
2H
2
O using magnetic suscep-
tibility, specic heat, and NMR measurement and did not
nd any sign of long-range order or a spin-gapped singlet
ground state down to T = 1.8 K. The ground state en-
ergy per bond calculated using coupled cluster technique
is equal to E
gs
/bond = 0.2126
We summarize the 2D S = 1/2 HAF on model lattices
that were reviewed in this section as follows:
S = 1/2 AFs on non-frustrated lattices possess semi-
classical Neel order. An energy gap vanishes in the
thermodynamic limit and the low-lying excitation
evolves into a Goldstone mode.
Quantum uctuations reduce the order parameter
and the degree of quantum disorder depends on com-
peting interactions between adjacent spin sites and
on the coordination number.
The semi-classical Neel order is weak in frustrated
lattices and it is not present in the kagome lattice,
possibly because a quantum spin liquid is the ground
state for this case. The kagome lattice could also
reveal a purely quantum VBC ground state.
1.1.2 Eects of applied eld on S = 1/2 Heisenberg antiferromag-
nets
Here we discuss eects of a magnetic eld applied to the model spin lattices examined above.
A nite magnetic eld orients spins towards the eld direction, thus breaking the planar
Figure 1.4: (a) Magnetization calculated of the S = 1/2 HAFM on a square lattice. The
open circles shows the data obtained by 1/S series expansion calculation, the dashed and
solid line are the results of the rst and second order spin-wave theory, respectively. (b)
Magnetization of the S = 1/2 HAFM on a triangular lattice in the presence of an external
magnetic eld of strength . The results of coupled cluster method (LSUB4, LSUB6 and
LSUB8) are compared with exact diagonalization (ED). The plots (a) and (b) are taken from
[35] and [40], respectively.
spin alignment, which may be the ground state at zero eld. In this sense, the presence
of an external magnetic eld can be viewed as a competing interaction, which can aect
quantum uctuations. Moreover, a magnetic eld gives the possibility to tune the ground
state and move the spin systems towards a quantum critical point (see Sec. 1.2). As we already
mentioned, S = 1/2 square-lattice HAF orders at zero temperature. Quantum Monte Carlo
calculations [32] have shown that applied magnetic eld induces a transition from Heisenberg
towards XY antiferromagnetic phase and leads to a nite temperature Berezinskii-Kosterlitz-
Thouless transition [33, 34], which is associated with an appearance of 2D topological spin-
vortices.
Fig 1.2(a) shows the magnetization calculated for the S = 1/2 HAFM on a square lattice
as a function of the applied eld. The data obtained by 1/S series expansion calculations
[15] are in a good agreement with rst- and second-order spin wave theory calculations
performed by Zhitomirsky and Nikuni [35]. The magnetization as the function of applied
eld for the classical model is represented by the straight line. The observed deviations seen
in Fig 1.2(a) are caused by quantum eects. Only little is known experimentally about the
eects of application of high magnetic elds on the excitation spectra for 2D AFs [36, 37]
- in contrast to 1D AFs. First predicted by Zhitomirsky and Chernyshev [36] and later by
L uscher and L auchli [38], the single-magnon excitation in S = 1/2 square-lattice AF overlaps
with a two-magnon continuum leading to instability of the former in high magnetic eld,
above H
c
0.76 H
sat
, where H
sat
is the saturation value. Experimental investigations of
the excitation spectra at 0.76 H
sat
have so far been impossible, because high exchange
interactions between adjacent spin sites imply the application of unreachable high magnetic
elds in real 2D systems.
A similar smooth dependence of the magnetization on the external magnetic eld was
found for the S = 1/2 HAF on a honeycomb lattice [39]. Upon application of magnetic
eld, the collinear antiferromagnetic order is canted towards the eld direction. Besides the
Goldstone mode associated with unbroken rotational symmetry in the honeycomb plane, a
gapped mode appears in the excitation spectra. Further, the system undergoes a eld-induced
phase transition from canted antiferromagnetic towards ferromagnetic state with the spins
aligned along the eld direction at H
sat
.
The magnetization as function of applied magnetic eld for the S = 1/2 HAF on a
triangular lattice is shown in Fig 1.2(b) [40]. These data were obtained by the coupled
cluster method and compared to the result of the exact diagonalization on N = 36 spin sites.
The most pronounced features in the magnetization curves for 2D triangular lattices is the
plateau at m = 1/3 [40, 41]. In the particular case of a triangular lattice, the nature of the
plateau can be understood in the Ising limit: the quantum uctuations are suppressed and
the state with m = 1/3 corresponds to the classical arrangements of spins pointing up in
two sublattices and down in third one, so called up-up-down state (see Fig. 1.4(b)). The
magnetization plateaus at one-third of the saturation eld for the Ising and Heisenberg limits
are qualitatively the same [41]. The appearance of the magnetization equal to m = 1/3 at
the nite range of applied magnetic eld is governed by quantum uctuations [42] which
stabilizes the collinear phase. Calculated by Chubukov and Golosov, the excitation spectra
of the S = 1/2 HAF on a triangular lattice has three resonant modes in magnetic elds below
the saturation value [42].
Numerical calculations [41, 43, 44] predict several features in a magnetization curve of
S = 1/2 HAF on a kagome lattice. Due to the absence of the Neel order, the magnetization
1.2 Quantum phase transitions 9
curve should have a at region at small applied elds. A second plateau is predicted to occur
at m = 1/3, similar to the case of a triangular lattice [45, 46]. This feature implies that the
system is in the ordered state, analogous to up-up-down state which emerges in a triangular
HAF at one-third of the magnetization [45]. A huge jump in the magnetization curve appears
in S = 1/2 HAF on a kagome lattice close to the saturation eld.
Under certain conditions, an applied magnetic eld can steer a spin system into a novel
quantum phase. We take a closer look on this case in the next section.
1.2 Quantum phase transitions
A classical phase transition (CPT) involves thermal uctuations occurring at nite tempera-
tures only. In the thermodynamic limit at T = 0 K, where the thermal energy scale is absent
only the uctuations associated with the Heisenberg
s uncertainty principle may be present.

In some cases those zero-point uctuations lead to transitions which, in analogy to CPT, are
called quantum phase transition (QPT) and occur at T = 0 K. In analogy with temperature
driven CPT, every QPT is governed by an external parameter, for instance magnetic eld or
pressure.
A system approaches a quantum critical point (QCP) in the thermodynamic limit under
application of the external parameter. Every continuous QPT is characterized by an order
parameter: Being zero in disordered phase an order parameter becomes non-zero while a
system reaches a QCP. Correlations of the order parameter diverges as [[ [t[
in the
vicinity of QCP. Here t is a measure of closeness to the QCP and is the correlation length
critical exponent. An order parameter uctuates not only in space but also in time. Close to
the QCP corresponding time correlations t
c
diverges as t
c
[t[
z
, where z is the dynamic
critical exponent.
Critical length and time scales are the only characteristics of the system close to QCP.
Scaling observable variables, all critical exponents depend on and t
c
exclusively. There-
fore the scaling is universal and depends only on the symmetry of the order parameter.
Consequently, QPTs can be classied by the symmetry of order parameter which forms the
universality class. It means that all observable variables in various QPTs posses a universal
behavior which can be described by a model system with a corresponding symmetry of the
order parameter [47, 48].
Importantly for experimental physics, quantum ordered phases occurring at T = 0 K
survive to a nite temperature range. This makes empirical investigations of QPT possible. A
wide range of QPTs was discovered: from superuid helium and the cuprate superconductors
which can be tuned from a Mott insulating to a superconducting phase by a carrier doping
[49, 50, 51] to various QPTs in quantum magnets and unconventional metals [52, 53]. The
main role in the phenomena is played by electrons and their collective behavior. Quantum
magnets, i.e. systems with localized electrons in reduced dimensions, belong to the most
important candidates for investigations of novel quantum phases. In the following sections
1.2.1 and 1.2.2 we introduce two specic examples of QPT in low-dimensional magnets.
1.2.1 Bose-Einstein condensation of magnons in quasi-1D systems
Here we show that a eld induced QPT from paramagnetic to the 3D XY ordered antifer-
romagnetic phase can be mapped onto Bose-Einstein condensation of magnons (BEC) in
axially symmetric magnets. The starting point is the spin Hamiltonian of the system, which,
for instance, in case of well studied spin-1/2 ladders [54, 55, 56, 57] can be written as
H = J
rung
rung
S
1,rung
S
2,rung
+ J
leg
i,j
S
i
S
j
g
B
H
k
S
z
k
, (1.2)
where the rst sum is taken over all rungs in spin ladder, the second sum runs over all legs
and the third term describes the impact of the magnetic eld H and its sum runs over all
spins in the system. We assume that the rung exchange interaction, J
rung
, is the strongest in
Eq. 1.2, coupling S
1
and S
2
into dimers. Thus the system eectively consists of interacting
S = 1 particles. Using second order quantization it was shown [55, 58] that Hamiltonian in
Eq. 1.2 can be mapped onto the following form
H =
i
(J
rung
g
B
H)a
+
i
a
i
+
i,j
t
ij
a
+
i
a
j
+
1
2
i,j
U
ij
a
+
i
a
+
j
a
i
a
j
, (1.3)
where the operators a
+
i
and a
i
create and annihilate a boson on dimer i, respectively, t
ij
describes a hopping between sites i and j and U
ij
is a repulsion energy. The coupling of
the transverse, S
x
i
S
x
j
+ S
y
i
S
y
j
, and longitudinal, S
z
i
S
z
j
, components in the spin Hamiltonian
in Eq. 1.2 map onto the hopping t
ij
and repulsion U
ij
terms in the bosonic representation
in Eq. 1.3, respectively. The singlet S = 0 is the ground state of the system described by
the Hamiltonian in Eq. 1.2 and is separated by a nite energy gap from the exited triplet
S
z
= 0, 1. An applied magnetic eld induces the Zeeman splitting and lowers the energy
of the dispersive S
z
= 1 excitation. When the eld energy is equal to the value of the gap,
g
B
H
c1
= , the excitation S
z
= 1 mixes with the ground state and the system undergoes
the QPT from quantum paramagnetic to the 3D antiferromagnetically ordered state. In the
bosonic representation, this process can be viewed as a condensation of magnons carrying
S = 1 and thus obeying Bose-Einstein statistics [59, 60]. In spin space, the eld-induced
Bose-Einstein condensation (BEC) of magnons corresponds to the order of the transverse
spin components, perpendicular to the applied eld, which spontaneously brakes the O(2)
symmetry of Hamiltonian Eq. 1.2. The list of the respective parameters of Bose gas and
quantum antiferromagnet is given in Tab. 1.2 [61]. The upper critical dimension d
c
and dy-
namical exponent z of BEC are equal to two. However the magnetically quantum ordered
phase exists at nite temperature region and its dimension is d > 2. Therefore, the experi-
mentally observed eld-induced phase transition at low-temperature region corresponding to
the BEC of magnons belongs to the 3D XY universality class with d = 3 and z = 2.
Bose gas Antiferromagnet
Particles Magnons carrying spin-1
Boson number N Spin component S
z
Charge conservation U(1) Rotational invariance O(2)
Condensate wavefunction
i
(r) Transverse magnetic order S
x
i
+ iS
y
i
Chemical potential Magnetic eld

Table 1.2: The respective parameters of Bose gas and quantum antiferromagnet. The table
is adopted from the review of T. Giamarchi et al [61].
The rst theoretical investigations of a possible BEC of magnons in quasi-one-dimensional
Figure 1.5: The schematic representation of the eld driven Bose-Einstein condensation of
magnons. The gure is taken from [56].
systems was discussed by E. G. Batyev, L. S. Braginskii [62] and I. Aeck [63, 59]. More
than fteen years later the process of the eld induced antiferromagnetic order was observed
experimentally in the gaped S = 1/2 compound TlCuCl
3
by A. Oosawa and co-workers
[54] and explained as the BEC of magnons by N. Nikuni et al [55]. The magnetization
measurements [54, 64] have shown that the magnetic subsystem of TlCuCl
3
consists of weakly
antiferromagnetically coupled S = 1/2 spin dimers and the rst excited state is separated
from the ground state singlet by the energy gap 0.7meV. At the quantum critical point,
which corresponds to the critical magnetic eld H
c
5.7T, the energy gap collapses.
The diagram of the eld induced QPT from magnetically disordered towards 3D XY an-
tiferromagnetic state is shown in Fig. 1.5. The solid line corresponds to the Zeeman splitting
of the excited triplet state. At the quantum critical point, the triplet mode S
z
= +1 reaches
the nonmagnetic ground state S
z
= 0 and the system turns into a 3D antiferromagnetic state,
which is proved by the detected Goldstone modes [57].
The isostructural material KCuCl
3
with coupled S = 1/2 dimers also undergoes eld
induced BEC of magnons. The energy gap is equal to 2.6 meV in this compound
[64], implying an application of a magnetic eld H 23 T to be closed. The magnon
condensate was also observed in many spin dimer compounds, as for example NH
4
CuCl
3
Figure 1.6: (a) Nearest and next nearest neighbor exchange interactions are shown by solid
and dashed lines, respectively. (b) The J
1
J
2
phase diagram [74].
[65, 66], Cs
3
Cr
2
Br
9
[67], BaCuSi
2
O
6
[68, 69], Cu(NO
3
)
2
2.5D
2
O [70], (CH
3
)
2
CHNH
3
CuCl
3
[71, 72]. The BEC of magnons is possible in other systems as well, for example in iron based
AFeX
3
(A is Cs, Rb and X is Cl, Br) compounds with hexagonal arrangement of spins [73].
1.2.2 Quantum phase transitions in 2D square-lattice antiferro-
magnets
As it was discussed in section 1.1, most of the 2D S = 1/2 HAFs adopts semi-classical long-
range order in the ground state. However the presence of quantum uctuations can suppress
this order. In the case of non-frustrated lattices, for instance a square lattice, quantum
uctuations can be enhanced by competing interactions between the nearest neighbor (NN)
and the next-nearest neighbor (NNN) spins. In literature this model is known as J
1
J
2
model, where J
1
and J
2
refer to NN and NNN exchange interaction, respectively, as it is
illustrated in Fig. 1.6(a). A frustrated square lattice with S = 1/2 is a simple example of
the spin system where competing interactions can lead to a completely disordered ground
state, i.e. to a spin liquid state. Fig 1.2(b) [74] shows the summarized diagram of the
ground states as the function of ratio J
2
/J
1
. Three main regions in the phase space are
occupied by semi-classical Neel order, ferromagnetic state and the columnar AF (CAF) state
for 0.4 < J
2
/J
1
< , < J
2
/J
1
< 0.4 and 0.7 < J
2
/J
1
< 0.7, respectively.
CAF phase can be viewed as collinear and anticollinear arrangements of magnetic moments on
a nearest sites, which form columns of spins aligned in one direction, as shown schematically
in Fig. 1.6(b) and Fig. 1.7. From the classical point of view, the phase transitions from Neel
order towards CAF and from CAF towards a ferromagnetic order occur at J
2
/J
1
= 0.5 and
J
2
/J
1
= 0.5, respectively (see Tab. 1.3 for details).
Ground state Wave vector Range (J
1
, J
2
)
NAF (, ) J
1
> 0, J
2
< J
1
/2
CAF (, 0), (0, ) [J
2
[ > [J
1
[/2
FM (0, 0) J
1
< 0, J
2
< J
1
/2
Table 1.3: Parameters for classical ground states in the J
1
J
2
model.
Numerous theoretical investigations for the J
1
J
2
model were performed for the most
interesting and less understood quantum critical regions, which are shown as hatched sectors
in Fig. 1.6(b). The boundaries of the critical phases are not known de facto. The quantum
spin liquid ground state described by the RVB state was proposed by Anderson [75] and
Kivelson et al [76]. Later, based on the 1/S series expansion calculations, Chandra and
Doucot [77] predicted a collapse of the Neel order at the critical ratio J
2
/J
1
0.38. The
numerical studies performed by Gelfald, Singh and Huse [78] gave a similar result, which
forecasts a QPT at J
2
/J
1
0.41 and the magnetically disordered state, where spins are
spontaneously dimerized in a columnar pattern for 0.41 < J
2
/J
1
< 0.64 (see Fig. 1.7).
A more complex structure of a quantum disordered state with several QPTs was pro-
posed by Sushkov and colleagues [79]. The result of the calculations yields four quan-
tum critical points for the ratio J
2
/J
1
equal to (J
2
/J
1
)
1
= 0.34(0.04), (J
2
/J
1
)
2
0.38,
(J
2
/J
1
)
3
= 0.5(0.02) and (J
2
/J
1
)
4
0.6. Fig. 1.7 shows schematically a summarized phase
diagram for 0 < J
2
/J
1
< 0.7 based on the results of Sushkov et al. A second order phase
transitions from Neel order to Neel state with columnar dimerization is predicted to occur at
(J
2
/J
1
)
1
. When the ratio J
2
/J
1
is increased further, the system undergoes a QPT to dimer-
Figure 1.7: The phase diagram of the S = 1/2 AF on a square lattice as the function of
g = J
2
/J
1
based on the series expansion calculations of Sushkov et al [79].
ized spin liquid and to a columnar dimerized spin liquid with plaquette type modulation at
(J
2
/J
1
)
2
and (J
2
/J
1
)
3
, respectively. The QPT towards CAF is predicted to be of rst order.
The discussion of the possible spin congurations in the quantum disordered phases for the
0.38 < J
2
/J
1
< 0.6 lies beyond the scope of this summary. Nevertheless, it is important to
emphasize that the suggested QPT can occur even for small variations of the J
2
/J
1
param-
eter. Theoretical investigations performed by Siurakshina, Ihle and Hayn [80] suggest the
transition from Neel and CAF states towards the quantum spin liquid phase at J
2
/J
1
= 0.24
and J
2
/J
1
= 0.83, respectively. In contrast to their study, recent calculations based on the
coupled cluster method [81] demonstrate the existence of the paramagnetic ground state for
0.44(1) < J
2
/J
1
< 0.59(1). The discrepancies in the theoretical studies indicate the necessity
of further explorations in this eld.
Recently the inuence of ferromagnetic NNN interactions on the J
1
J
2
model was
studied. Nematic order in the AF on a square lattice with a ferromagnetic J
2
was predicted
by numerical calculations of Shannon et al for J
2
/J
1
0.5 [82]. The authors found a rst
order transition from the saturated ferromagnetic ground state to a gapless spin-liquid state
with bond-nematic order.
However, in contrast to the theoretical studies in this eld, the experimental realizations
of J
1
J
2
models on a square lattice are quite rare. We will briey discuss the main layered
vanadium oxide based materials, which have attracted researchers for the last decade (see
Fig. 1.6). The rst J
1
J
2
model was experimentally realized in VoMoO
4
and studied by high-
resolution x-ray and neutron powder-diraction [83]. The ordered magnetic moment in the
semi-classical Neel ground state is equal to m = 0.41(1)
B
/V
4+
, which indicates enhanced
quantum uctuations due to NNN interactions J
2
/J
1
0.2. Another good experimental
realization of the J
1
J
2
model is Li
2
VOX
i
O
4
(X
1
= Si, X
2
= Ge). These materials were
studied experimentally using specic heat and susceptibility measurements, NMR [84, 85].
It was found that the systems have ratios of the NNN to NN exchange interaction equal
to J
2
/J
1
12 and J
2
/J
1
4.8 for silicon and germanium components, respectively. The
measurements also revealed the nite interlayer coupling of J
2
/J
0.02 and J
2
/J

0.03. The ordered magnetic structure and the ordered magnetic moment in Li
2
VOSiO
4
was
determined by neutron diraction and resonant x-ray scattering measurements [86]. The
magnetic moment in collinear antiferromagnetic ground state is equal to m = 0.63(3)
B
, and
is thus very close to the value expected for the 2D Heisenberg model.
Recently synthesized layered perovskite PbVO
3
is the realization of a highly frustrated
J
1
J
2
model. The material was studied by measuring the temperature dependence of the
magnetic susceptibility and the specic heat [87, 88]. The results show that the frustration
ratio is equal to J
2
/J
1
0.3, indicating its proximity to the critical region which separates a
simple Neel state and Neel state with columnar dimerization (see Fig. 1.6).
The behavior of the 2D S = 1/2 AF in magnetic elds was studied theoretically for the
case J
1
J
2
model [89, 90]. However, little is known experimentally about the magnetic eld
behavior of the 2D S = 1/2 AF, particularly in the presence of NNN interactions.
1.3 Summary 17
1.3 Summary
In conclusion, we reviewed a range of important 2D spin lattices and discussed the presence of
quantum uctuations due to reduced dimensionality. Zero-point uctuations in such systems
can lead to purely quantum VBS and spin liquid ground states. An external magnetic
eld enhances or suppresses the quantum uctuations providing the fascinating possibility of
tuning and controlling interactions in the quantum limit. Moreover, it can turn the a spin
system into novel quantum phases, providing unique possibilities for an investigation of novel
aspects of quantum matter.
1.4 Structure of the thesis
The thesis is organized in the following way.
Chapter 2 is devoted to the experimental technique. Being the prime experimental
method of our work, neutron scattering is discussed here. The instrumentation and
important parts of a sample environments extensively used in our experiments, such as
three-axis spectrometers split-coil magnets and dilution refrigerators, are described in
the same chapter as well.
Comprehensive study of a weakly-frustrated 2D S = 1/2 AF on a square lattice realized
in the organo-metallic compound Cu(pz)
2
(ClO
4
)
2
is presented in the Chapter 3. We
determine the eld-temperature phase diagram for magnetic elds up to one-third of
the saturation value and investigate the symmetry of the ordered magnetic phase.
The magnetic excitation spectra measured by inelastic neutron scattering in zero and
applied magnetic elds are presented and explained based on a precisely determined spin
Hamiltonian. Moreover we prove experimentally that quantum uctuations associated
with RVB state exist in the S = 1/2 square lattice AFs and enhanced by a small
additional NNN interaction between spins.
In Chapter 3 we concentrate on strongly anisotropic quasi-one-dimensional S = 1 chain,
NiCl
2
4SC(NH
2
)
2
, and discuss the investigations of this material using both elastic and
inelastic neutron scattering. Determined ordered antiferromagnetic structure has a
collinear spin alignment with a preserved rotational symmetry. The size of the ordered
magnetic moment is estimated as a function of eld-temperature from the neutron
diraction measurements. The magnetic phase diagram is determined using neutron
diraction in coordinates eld-temperature. We show that the magnetic eld applied
parallel to the spin chain closes the energy gap between the ground state and the
excited doublet, which can be described as BEC of magnons. The spin Hamiltonian
is established, based on our neutron spectroscopy experiments performed in a fully
magnetized phase of DTN. The spin dynamics in the antiferromagnetic phase is also
discussed.
Chapter 2
Neutron scattering
2.1 Main properties of the neutron
The existence of a neutral subatomic particle suggested by Lord Ernest Rutherford in the
1920
ies
was conrmed by the important discovery of the neutron by James Chadwick in
1932 [91, 92, 93]. Later, the possibility of Bragg diraction of neutrons was demonstrated
[94] and neutron scattering became one of the most important and multifaceted techniques
in condensed matter research. The main properties of the neutron are listed in Tab. 2.1.
Due to the absence of electrical charge, and thus a lack of Coulomb interactions between
charged particles and a neutron, the neutron can penetrate deep into solids and interact
with the bulk. Having a spin of one-half and an associated magnetic moment, neutrons obey
Fermi-Dirac statistics. Therefore, the combination of the chargeless nature and the presence
of a magnetic moment gives an unique opportunity for experimental investigations of bulk
magnetic structures and excitations in condensed matter using neutron scattering.
2.1.1 Neutron sources
Neutron scattering research facilities are based on either a nuclear reactor or a spallation
source. A nuclear reactor uses spontaneous ssion of
235
U for creating a high-ux of neutrons.
A spallation source produces particles by bombarding a heavy metal target with high-energy
protons. The neutron beam produced in nuclear reactors is continuous, while spallation
20 Neutron scattering
Quantity Value
Mass 1.67492729(28) 10
27
kg
Charge 0
Spin 1/2
Magnetic moment 9.6623640 10
27
J/T
decay n p
+
+ e
+
Life time 888(3) s
Table 2.1: Main characteristics of neutron.
sources provide typically a pulsed neutron beam. The most powerful research reactors is the
High Flux Reactor (HFR) at the Institute Laue-Langevin (ILL), France, and provides a ux
of I 10
15
neutrons/(cm
2
sec) with a thermal power of W 58.3 MW. Continuous spallation
sources produce usually a ux of one order of magnitude lower compared to nuclear reactors.
The highest value of peak neutron ux equal to I 3 10
16
neutrons/(cm
2
sec) is generated
by a pulsed spallation sources SNS. Another example of the spallation neutron source, ISIS,
produces a peak ux of I 6 10
15
neutrons/(cm
2
sec).
The Swiss Spallation Source (SINQ) located at Paul Scherrer Institute (PSI), Villi-
gen, Switzerland, is based on a 590 MeV Ring Cyclotron, whose accelerator frequency
= 50.63 MHz. Such a high frequency provides the possibility to smear out a pulsed
neutron ux and to obtain a continuous nal beam.
In order to be useful for scattering experiments, high-energy neutrons obtained after the
spallation process or nuclear reactions are cooled down by passing a moderator block. A
wide distribution of neutron energies results from a use of three main moderators. Containing
liquid deuterium cooled down to T 20 K, a cold moderator has the maximum transmission
for neutrons with energies E 5 meV. Providing uxes of neutrons with energies E
25 meV, thermal moderators are made out of heavy and light water for spallation sources
and nuclear reactor, respectively. Finally hot moderators uses heated up graphite to speed
up thermal neutrons and obtain the energies of order E 200 meV.
After the moderator block the ux is usually transported to an experimental instrumen-
tation by neutron guides. Acting on neutrons like supermirrors, guides are conventionally
2.1 Main properties of the neutron 21
made out of polished glass coated with special materials, for instance Ni-Ti. Neutron guides
installed at SINQ or SNS include the supermirrors which have been produced using DC-
magnetron sputtering: The mirror consist of a top layer of nickel and a sequence of 100
layers Ni-N-O/TiVx diracting neutrons by Bragg reection. In this way the neutron ux
can be transported into relatively big distances ( 100 meters) with small losses. A perfor-
mance of instruments based on neutrons transported by guides, implies usually the use of
cold neutrons and naturally small background scattering (less than 10
1
counts per minute).
In contrast, instruments located in close vicinity to a neutron source ( 10 meters) without
a neutron guide, are designed to work in thermal - epithermal regimes and have a higher
background scattering, more than 10
1
counts per minute.
2.1.2 Energy and time scales
The mass of a neutron m
n
and the velocity v are related to its De Broglie wavelength and
the wave-vector k by m
n
v = hk = h/. Therefore, the total energy of a neutron is equal to
E =
m
n
v
2
2
=
h
2
[k[
2
2m
n
. (2.1)
The generally accepted classication of neutron energy ranges is presented in Tab. 2.2. Scat-
tering experiments using cold and thermal neutrons can probe a wide range of properties
in solids, including crystal and magnetic structures, lattice vibrations and anharmonicities,
spin-waves and crystal elds among many others. Therefore, most large scale facilities are
designed to produce a high-ux in cold and thermal regimes. The velocity of thermal neu-
trons is equal to v 2.2 km/s corresponding to an energy E = 25.3 meV, the temperature
T = 293 K and the wavelength = 1.798

A.
A neutron scattering process is shown schematically in Fig. 2.1. The incoming particle
with wave vector k
i
scatters at the single crystalline sample and changes direction by an
angle of 2 to the initial direction. Momentum and energy conservation of the scattering
process leads to the following equations:
hQ = hk
f
hk
i
,
Classication Energy
Epithermal (K) 250 10
3
meV
Hot 200 meV
Thermal 25 meV
Cold 5 10
2
25 meV
Very cold 3 10
4
5 10
2
meV
Ultra cold < 3 10
4
meV
Table 2.2: Energy classication of neutrons.
h = E
i
E
f
=
h
2
(k
2
f
hk
2
i
)
2m
n
, (2.2)
where indexes i and f correspond to initial and nal (scattered) states, respectively, hQ is
the momentum transferred to the sample. A scattering process is called elastic in the case of
a zero energy transfer and usually it is used to determine a crystal or magnetic structures.
The scattering process with a non-zero energy transfer is called inelastic, and is used to
probe dynamic features of crystal or magnetic structures. Both elastic and inelastic neutron
scattering processes are discussed below. For further details, a number of good textbooks are
recommended [95, 96, 97, 98].
2.2 Elastic neutron scattering
2.2.1 Fermis Golden rule
Being the fundamental concept of any scattering process, the cross-section describes an eec-
tive area for collision. In order to set the experimental stage, we have to dene the neutron
scattering cross-section. Suppose, neutrons with a certain energy E
i
scatter on the sample
into the given direction into the solid angle . In this case the scattering rate is dened
as (k
i
), where (k
i
) is the initial ux of neutrons with the wave vector k
i
and is the
cross-section. Technically, neutron scattering experiments are based on measurements of a
double dierential cross-section assigned as a number of scattered neutrons per solid angle
2.2 Elastic neutron scattering 23
Figure 2.1: Scattering process.
d
f
and per energy range from E
f
to E
f
+ dE
f
. It can be written as the sum of coherent
and incoherent parts:
d
2
d
f
dE
f
=
d
2
d
f
dE
f
coh
+
d
2
d
f
dE
f
inc
(2.3)
The rst term, coherent, describes collective eects in many body systems, like nuclear or
magnetic Bragg diraction and inelastic scattering from magnons or phonons. The incoherent
term physically arises from deviations of nucleus from their positions dened by a crystal
symmetry, for instance due to thermal uctuations or diusion processes. Our scientic
interest lies in the eld of collective eects in solid state and from now on only the coherent
part of the double-dierential cross-section will be taken into account. Incoherent scattering
results in a background which we try to eliminate.
In quantum physics, the probability of the transition of the system from one eigenstate
[i to another [f per unit time is dened by the Fermis Golden rule. Assuming that U is
the operator which describes the interaction of a neutron with the system and taking into
account the Fermis Golden rule, we can write the double-dierential cross-section as follows:
d
2
d
f
dE
f
=
k
f
k
i
(
m
n
2 h
2
)
2
[k
f
f
[U[k
i
i
[
2
( h + E
i
E
f
), (2.4)
where
i
and
f
are quantum numbers corresponding to initial and nal states, respectively.
2.2.2 Nuclear scattering
Nuclear scattering is the result of the short-range ( 1 fm) interaction between a nucleus and
a neutron. Starting from Eq. (2.4), we can write the double dierential cross-section which
describes the process as follows:
d
2
d
f
dE
f
= N
k
f
k
i
l
b
2
l
S(Q, ), (2.5)
where N is the number of scattered centers in the system and b
l
is the nuclear scattering
length of the nucleus l which depends on details of the neutron-nuclear interaction potential.
The neutron scattering function, S(Q, ), describes the contribution of a scattered system
into the coherent cross-section and it is dened as
S(Q, ) =
1
2 hN
ll
_
+
dte
iQr
l
(0)
e
iQr
l
(t)
e
it
, (2.6)
where the angle brackets denote the average over initial states, and the integral is taken over
time. Therefore, based on measurements of S(Q, ), appropriate microscopic properties of
investigated material can be determined.
Taking into account only elastic neutron scattering on a crystal, the scattering function
Eq. (2.6) can be written as
S(Q, ) = ( h)
(2)
3
K
(QK), (2.7)
where the sum is taken over the reciprocal lattice vectors K. Thus, using Eq. (2.5) and
Eq. (2.7), the elastic cross-section in a crystal medium is given by
d
d
= N
(2)
3
K
(QK)[F
N
(Q)[
2
, (2.8)
where F
N
(Q) is an important quantity called nuclear structure factor:
F
N
(Q) =
i
b
i
e
iQd
i
e
1
2
(Qu
i
)
2
, (2.9)
2.2 Elastic neutron scattering 25
describing positions d
i
and displacements u
i
of ions in a unit cell. From Eq. (2.8) we see that
elastic scattering occurs only if the moment transferred to the single crystal is equal to the
reciprocal wave-vector, Q = K. This is the case of Bragg diraction: satisfying Braggs law
n = 2d sin(), diracted peaks appear. Therefore, based on measured neutron diraction
patterns, i.e. the scattered intensities as a function of the angle , crystal structures of an
investigated material can be analyzed. It is important to note that various structural phase
transitions in solids can be detected by performing diraction measurements in dierent
environmental conditions, for instance, temperature or pressure.
2.2.3 Magnetic scattering
Due to the classical magnetic dipole-dipole interactions between neutron and magnetic mo-
ment of electron, neutron scattering also gives the possibility to probe bulk magnetic struc-
tures.
The amplitude for magnetic scattering can be written in the following form:
I
m
(Q) = (
r
0
2
)gf(Q), (2.10)
where r
0
is the classical electron radius, the gyromagnetic ratio, g the Lande splitting factor
and
f(Q) =
_

s
(r)e
iQr
dr
the magnetic form factor that is the Fourier transform of the normalized unpaired spin density
s
(r). Taking into account magnetic interactions, the dierential cross section Eq. (2.4) is
dened as follows:
d
2
d
f
dE
f
=
k
f
k
i
i,f
P(
i
)[
f
[
l
e
iQr
l
U
s
i
s
f
l
[
i
[
2
( h + E
i
E
f
), (2.11)
where U
s
i
s
f
l
is the scattering amplitude from spin site s
i
to s
f
on site l
U
s
i
s
f
l
= s
f
[b
l
p
l
S
l

n
+ B
l
I
l

n
[s
i
. (2.12)
Here b
l
is the nuclear coherent scattering amplitude,
n
Pauli spin operator for a neutron,
B
l
the spin-dependent nuclear amplitude and I
l
is the nuclear spin operator. The magnetic
interaction vector S
dened as S
= S Q(Q S) means that only spin components

perpendicular to the wave-vector Q will contribute to the magnetic scattering intensity.
Summarizing, we can write the magnetic dierential cross section in the following form:
d
2
d
f
dE
f
= (r
0
)
2
k
f
k
i
e
2W
[f(Q)[
2
,
(
,
Q
2
)S
,
(Q, ), (2.13)
S
,
(Q, ) =
i,j
e
iQ(r
i
r
j
)

i
,
f
p
i
[S
i
[
f
f
[S
i
[
i
( h + E
i
E
f
), (2.14)
where (
,

Q
Q
2
) is the magnetic polarization factor, S
,
(Q, ) the magnetic scattering
function and S
i
( = x, y, z) denotes the spin operator of i

th
ion located at r
i
. In the case
of elastic scattering on magnetically ordered crystals, (2.13) simplies to
d
d
f
= N
m
(2)
2
G
m
e
2W(G
m
)
(QK
m
)[F
m
(K
m
)[
2
, (2.15)
where the exponent is the Debye-Waller factor. In analogy with the nuclear structure factor
(2.9), the magnetic structure factor is dened as following:
F
m
(K
m
) =
j
p
j
S
j
e
iK
m
d
j
. (2.16)
The index m corresponds to the magnetic unit cell, which, generally speaking, can be dierent
from the nuclear one.
Therefore, using magnetic elastic neutron scattering, magnetic Bragg reections can be
measured and, generally, the ordered magnetic structure can be determined. Taking into
account the spin dependence of the magnetic amplitude M(Q) = gS
B
f(Q), the value of an
ordered magnetic moment can be estimated from a neutron scattering experiment.
2.3 Neutron spectroscopy 27
2.3 Neutron spectroscopy
In addition to the investigation of ordered nuclear and magnetic structures, neutron scattering
also allows the measurement of the dynamics of crystal lattices and magnetic frameworks in
bulk materials. In this section inelastic neutron scattering on nuclear and magnetic structures
are discussed.
2.3.1 Inelastic nuclear scattering
According to Eq. (2.2), a neutron can gain or lose energy while the particle scatters. This
process obeys universal principle of detailed balance
S(Q, ) = e
h/k
B
T
S(Q, ), (2.17)
which emphasizes properties of an equilibrium state and it is illustrated schematically in
Fig. 2.2. If neutron loses energy in the scattering process (Fig. 2.2(a)), the scattering system
becomes excited from the ground state to a higher-energy state
. This transition con-

tributes to the scattering function S(Q, ). Fig. 2.2(b) shows the reverse process in which
the scattered neutron gains energy and the transition in the scattering system contributes to
S(Q, ). The probability of the scattering system being initially in the low-energy state
is higher by e
h/k
B
T
then the probability of being in the high-energy state
.
The uctuation-dissipation theorem [99] is based on the assumption that in thermal equi-
librium the response of a system on a small perturbation is the same as its response on a
spontaneous uctuation. Therefore, the measured response of a thermodynamic system can
provide an information about its uctuation properties. According to this, the relation be-
tween the neutron scattering function and the imaginary part of the dynamic susceptibility
is
S(Q, ) =

(Q, )
1 e
h/k
B
T
. (2.18)
The signicance of this equation lies in the fact that the measured response of a system
(Q, ) can be compared directly to the theoretically predicted value, which often can be
Figure 2.2: Principle of detailed balance.
calculated from rst principles.
During inelastic scattering on an ordered atomic system, a neutron creates or destroys a
phonon. In this case the imaginary part of the dynamic susceptibility can be written in the
form
(Q, ) =
1
2
(2)
2
G,q
(Qq G)
s
1
qs
[F(Q)[
2
[(
qs
) ( +
qs
)] (2.19)
where F(Q) is the dynamic structure factor. Based on equation (2.19) phonon dispersion
can be measured by performing inelastic neutron scattering experiments.
2.3.2 Inelastic magnetic scattering
Collective spin excitations are called spin waves. The energy of a spin wave is quantized
1
and it has a Q-dependence which can be measured by inelastic neutron scattering. In anal-
ogy with phonons, during inelastic scattering in a magnetically ordered medium, a neutron
creates or destroys a spin wave. Assuming that a propagating spin wave is comprised of
spin displacements from an ordered direction in a ferromagnet, the double dierential cross
section Eq. (2.4) can be written for the case of inelastic magnetic scattering in the following
1
Quantized spin waves, or magnons, were described in terms of secondary quantization formalism by
Holstein and Primako [100] who had shown that magnons obey Bose-Einstein statistics.
2.4 Experimental technique 29
manner:
d
2
d
f
dE
= (r
0
)
2
k
f
k
i
(2)
3
2
0
S(1 + Q
2
z
)[F(Q)[
2
e
2W
q,G
[n
q
+ 1( h h
q
)(Qq G) +n
q
( h + h
q
)(Q+q G)], (2.20)
where n
q
= (exp(h
q
/k
B
T)1)
1
is the thermal average. Equation (2.20) demonstrates the
possibility to measure the dispersion of spin waves directly using inelastic neutron scattering.
Calculations of Q-dependence of the energy of spin waves is based on a magnetic ordering
geometry and symmetry properties of the system. For a relatively simple case of a two-
dimensional S = 1/2 AF with NN and NNN exchange interactions, the calculation of spin
wave dispersion in linear approximation is given in Appendix A.
2.4 Experimental technique
In the eld of inelastic neutron scattering, three-axis spectroscopy (TAS) together with time-
of-ight spectroscopy are the most common used techniques. While the rst technique pro-
vides a possibility to measure particular positions in (Q, ) space point-by-point, rather large
regions of phase space can be explored by the time-of-ight technique. However, the price
paid for a large phase-space probe by time-of-ight spectroscopy is that intensities on a sam-
ple are considerably reduced due to the use of a pulsed neutron beam. Since a major part of
results represented in this manuscript are obtained using TAS, the concept of this method is
describe below.
2.4.1 Three-axis spectroscopy
Fig. 2.3 shows a sketch of a typical three-axis instrument. The performance of the instrument
is based on Braggs law. First, passing through a guide, the neutron beam is scattered on
a monochromator crystal in the direction of the sample. Then the beam scattered on the
sample traverses the analyzer and comes to the detector. Monochromators and analyzers
are usually made of single crystals and serve to select and analyze neutrons with a specic
wavelength based on Braggs diraction law
n = 2d sin(). (2.21)
Here n is an integer number and represents the order of scattering, d is the distance between
planes in a crystal which cause the diraction of the beam in direction with the angle .
Figure 2.3: Three axis spectrometer. The combina-
tion of monochromator, sample and analyzer axes
provides a wide range of experimental possibilities
for condensed matter research.
Crystals can be bent or turned thus
that an appropriate change of d lead
to Bragg scattering of neutrons with
the selected wavelength . Single crys-
tals of pyrolytic graphite (PG), germa-
nium or silicon are commonly used for
monochromating and analysis of neu-
tron beams. In general high order
scattering exists and can be used for
measurements in restricted experimen-
tal conditions, however more often it
complicates experiments. In order to
suppress high order scattering, dierent
lters can be installed before or after
the sample. It is common to use PG,
beryllium or beryllium-oxide as high or-
der lters. When the neutron beam
with a chosen wavelength according to
Eq. (2.21) hits the sample, the scattered
intensities are distribute in dierent directions according to equation Eq. (2.4). An angular
dependence of the distribution can be probed by varying scattering angles between incoming
and scattered beams. Rotation of the analyzer denes the direction towards the detector
providing a possibility to obtain information about energy distribution of scattered neutrons.
Measured in this way the scattering function, S(Q, ), can be used to explore the nuclear or
magnetic structure and dynamic properties.
A substantially easier experimental method is based on the use of the monochromator and
the sample axis only and therefore it is called two-axis technique. The lack of the analyzer
indicates the impossibility to perceive a dierences between energies of neutrons scattered
on the sample leading to a higher background compare to the setup with the analyzer.
However, for some measurements this experimental limitation is irrelevant, for instance, the
case of diraction measurements.
In order to increase a neutron ux on a sample, an incoming beam can be focused by a
bendable monochromator crystal or several crystals mounted on independent holders. Ver-
tical focussing is resulted from the deformed monochromator crystals to a cylinder with its
axis lying in the horizontal plane. At the cost of wave-vector resolution, the gain in ux can
be achieved in this case. By focusing in both directions, vertical and horizontal, total neutron
ux on a sample can be increased by approximately hundred times. Analyzer crystals can be
focused in the same manner. The result of using focused analyzer is identical to making the
distance between analyzer and detector smaller. However an unfavored eect of the latter
option is an increased background due to a larger detector. In contrast, a use of focused
analyzer implicates a lower background.
2.4.2 The experimental resolution function
Heretofore, precisely dened wave-vectors of incoming and scattered beams and the scattering
angle were considered for neutron scattering experiments idealizing the actual situation. In
reality all three-axis spectrometers have a nite resolution due to the following reasons:
1. Any pathway of a neutron beam has nite divergences in directions perpendicular to
the ideal propagation direction.
2. Monochromator and analyzer reect neutrons with a very small, but nite spread of
wavelengths.
Therefore, detected neutrons are characterized by the incoming, nal wave-vectors and the
scattering angle distributed around the average values k
i
, k
f
and 2. Since those limita-
tions are caused by the experimental technique, the resolution depends only on the specic
instrumental conguration and is independent of actual physics of the studied sample.
As it was shown above (Sec. (2.2), (2.3)), the double-dierential neutron scattering cross-
section can be written as
d
2
d
f
dE
f
=
k
f
k
i
S(Q, ), (2.22)
with

S(Q, ) dened appropriately for a particular situation. Suppose the spectrometer is
set to the special point in the phase space (Q
0
,
0
) and three Cartesian coordinates Q
,
Q
and Q
z
are dened as parallel to Q
0
, perpendicular to Q
0
in the scattering plane and
perpendicular to the scattering plane of Q
0
, respectively. In this case the intensity I(Q
0
,
0
)
detected by the instrument can be calculated using the following four-dimensional integral:
I(Q
0
,
0
) =
_
R(QQ
0
,
0
)
S(Q, )d dQ. (2.23)

Relation (2.23) is very general and it shows that measurements performed at the particular
point (Q
0
,
0
) depend on the scattering function

S(Q, ) convoluted with the instrumental
resolution function R(QQ
0
,
0
), which is dened as
R(QQ
0
,
0
) = R
0
exp(1/2M). (2.24)
First derived by Copper and Nathans [101], this equation is based on the assumption that
the distributions of k
i
and k
f
are Gaussians. Here M is a four-dimensional function of k
i
, k
f
and 2, depending on all experimental parameters, including all lengths of beam pathways
between dierent parts of the instrument, vertical and horizontal divergences of the beam,
dimensions of the analyzer, the detector and the mosaicity of monochromator and analyzer.
is a vectorial parameter
= (Q
Q
0
, Q
, Q
z
,
m
n
hQ
0
(
0
)). (2.25)
The normalization factor R
0
used in equation (2.24) is based on all experimental parameters
as the matrix M. The constant amplitude prole for the resolution function is a set of nested
four-dimensional ellipsoids in (Q, ) space and it can be calculated using equations of the
form M = Constant. Size and shape of the resolution ellipsoid can be adjusted by
changing the experimental setup, however an increase of the resolution leads to a drop of
detected intensities. Therefore, one of the main experimental issues is to nd a compromise
between a good resolution and a reasonable time of the measurement by nding a proper
instrumental conguration of the spectrometer, which will lead to a good signal-background
ratio.
It is worth to mention that for the cases of focused monochromator and analyzer, the way
of calculating a resolution function diers from a at regime. First described by Cheeser and
Axe [102], R
0
and R(QQ
0
,
0
) for the focusing mode were calculated and alter math
was generalized by Popovici [103]. For further details concerning computing the resolution
function we refer to the original publications listed above and to the books written by Hippert
[104] and by Shirane, Shapiro, and Tranquada [97].
In contrast to the resolution analysis of the inelastic neutron data, resolution corrections
for the case of elastic experiments look much simpler. The examination of scattering observed
in a diraction experiment is conventionally based on the following function:
I(Q
0
) = C
1
+ C
2
0
+ m
hkl
[F[
2
L(
0
) exp
_
4 ln 2
_
2
0
2
hkl
0
_
2
_
, (2.26)
where C
1
and C
2
are the background parameters,
0
is the angle corresponding to the
observed Bragg peak, m
hkl
is the multiplicity of the reection, L(
0
) = 1/ sin sin 2 is the
Lorentz factor and the function
0
describes the lineshape of the peak:
0
=
_
U tan
2
0
+ V tan
0
+ W, (2.27)
where U, V and W are the parameters depend on the geometry of the experiment.
Finally, to perform a proper analysis of data obtained by TAS, an experimentalist must:
1. Determine the instrumental resolution function.
2. Convolute it numerically with a model (or expected) scattering function.
3. Fit the experimental data using resolution-convoluted function.
2.5 Sample environment
As we have shown in Sec. 2.2.3 and Sec. 2.3.2, the neutron scattering technique provides
an essential possibility to study magnetic properties of bulk materials. Magnetic phase
transition are driven by external thermodynamical parameters, for instance, by magnetic
Figure 2.4: The mixing chamber
of dilution refrigerator.
eld or temperature. In order to understand a mag-
netic phenomena in its entirety, neutron scattering ex-
periments can be performed in dierent external envi-
ronments. In this section we briey describe the main
concepts of split coil magnet and dilution refrigerator,
which were extensively used during the work on this the-
sis.
2.5.1 Split coil magnets
The discovery of type II superconductors made possible
a generation of high magnetic elds by means of super-
conducting magnets. Being superconducting in magnetic
elds, solenoids made out of those materials carry giant
currents producing high magnetic elds. Generally, split
coil magnets are based on niobium-titanium supercon-
ducting wires doped with epoxy, wrapped into a solenoid
and cooled with liquid helium and liquid nitrogen. Two
solenoids are placed on the same axis close to each other.
Therefore, a sample loaded in a small region between the
superconducting solenoids is accessible for incoming neu-
tron beam. To achieve high elds, (Nb, Ti)
3
Sn wires are
2.5 Sample environment 35
used in split coil superconducting magnets as an inner coil. The eld generated by a split coil
magnet has a technical limit B
lim
15 T, which was sucient for our experimental needs.
2.5.2 Dilution refrigerator
The usage of dilution refrigerator was essential for the experimental investigation of quantum
eects in low-dimensional magnets Cu(pz)
2
(ClO
4
)
2
and NiCl
2
4SC(NH
2
)
2
. Being a side eect
in this experimental work, thermal uctuations were suppressed by cooling the systems down
to a few tenths of milliKelvin in a dilution refrigerator. The operation of this complex device
is based on a mixture of two helium isotopes,
4
He and
3
He. At T 870 mK the mixture
spontaneously separates into
3
He rich and diluted phases. The mixing chamber is shown
schematically in the Fig. 2.4. Helium atoms in the diluted phase are attracted to each other
by Van der Waals forces stronger compare to ones in the reached phase. As the result,
3
He reached phase is approximately 20% less dense than diluted one. In the process of
phase separation, the system looses energy while transporting
3
He atoms from the reached
to the diluted phase. Providing a continuous stream of
3
He atoms into the reached phase
and, therefore, a permanent ow of
3
He atoms crossing the phase boundary line, dilution
refrigerator cools down to milliKelvin temperature range.
2.6 Summary
In this chapter the essence of neutron scattering and remarkable opportunities, provided by
this experimental technique for condensed matter research, are described. A wide range of
solid state characteristics can be probed by neutron scattering including ordered crystal and
magnetic structures, lattice dynamics and magnetic excitations, phase transitions and critical
magnetic behavior. TAS - a powerful tool for investigations of excitations in bulk solids and
the instrumental resolution function are discussed.
Chapter 3
2D S = 1/2 antiferromagnet on a
square lattice Cu(pz)
2
(ClO
4
)
2
3.1 Introduction
As it is discussed in Chapter 1, the ground state of the 2D S = 1/2 square lattice Heisen-
berg AF adopts Neel long-range order at zero temperature. Nevertheless, strong quantum
uctuations arising from geometrical frustration may destroy long-range order in 2D. Even
in the absence of frustration, numerical studies of the 2D S = 1/2 Heisenberg AF on a
square lattice using quantum Monte Carlo, exact diagonalization, coupled cluster as well as
series expansion calculations reveal a quantum renormalization of the one-magnon energy
in the entire Brillouin zone and the existence of a magnetic continuum at higher energies
[12, 13, 11, 14, 15]. In recent years, quantum renormalization eects at zero eld have been
studied using neutron scattering in a number of good realizations of S = 1/2 square-lattice
Heisenberg AFs [105, 106, 107, 108, 109, 110].
The addition of antiferromagnetic NNN interactions destabilizes the antiferromagnetic
ground state and increases quantum uctuations (see Chapter 1): according to the J
1
J
2
model [77, 112, 113, 114], where J
1
and J
2
are the NN and the NNN exchange interactions,
respectively, dierent ground states are stabilized as a function of J
2
/J
1
. A possible spin-
liquid phase appears to be the ground state for 0.38 < J
2
/J
1
< 0.6 and collinear order was
found computationally for J
2
/J
1
> 0.6 (see Sec. 1.3).
2
(ClO
4
)
2
The behavior of the 2D S = 1/2 AF in magnetic elds was studied theoretically for
the case of nearest neighbor interactions [35, 36, 37] as well as for J
1
J
2
model [90, 115].
However, little is known experimentally about the magnetic eld behavior of the 2D S = 1/2
AF, particularly in the presence of next-nearest neighbor interactions.
In this chapter we present an experimental investigation of the 2D organo-metallic AF
Cu(pz)
2
(ClO
4
)
2
, a good realization of the weakly frustrated quantum AF on a square lattice
with J
1
1.56 meV. Due to the small energy scale of the dominant exchange interaction,
magnetic elds available for macroscopic measurements and neutron scattering allow the ex-
perimental investigation of this interesting model system for magnetic elds up to about one
third of the saturation eld strength. We combine specic heat, neutron diraction and neu-
tron spectroscopy to determine the spin Hamiltonian and the key magnetic properties of this
model material. Specic heat measurements show that the magnetic properties are nearly
identical for elds applied parallel and perpendicular to the square-lattice plane. This shows
that spin anisotropies are small in contrast to spatial anisotropies, and that it is sucient
to perform microscopic measurements for just one eld direction. Our microscopic neutron
measurements, on the other hand, provide information on the spin Hamiltonian that explain
the nearly identical eld-temperature (HT) phase diagrams for the two eld directions. Spe-
cic heat and neutron measurements of Cu(pz)
2
(ClO
4
)
2
thus ideally complement each other.
Moreover, we show that even a small J
2
/J
1
0.02 ratio enhances quantum uctuations
drastically, leading to a strong magnetic continuum at the antiferromagnetic zone boundary
and the inversion of the zone boundary dispersion in magnetic elds.
3.2 Bulk properties
3.2.1 Crystal structure.
For several decades, copper pyrazine perchlorate, Cu(pz)
2
(ClO
4
)
2
, has been held to be a good
realization of the 2D S = 1/2 AF [116]. Synthesized from a solution of Cu(ClO
4
)
2
6H
2
O,
pyrazine (C
4
H
4
N
2
) and HClO
4
, single crystals of Cu(pz)
2
(ClO
4
)
2
have rectangular shape and
layered structure. Typical crystals are shown in Fig.3.1(c) and were grown within a period
of one week. At room temperature, Cu(pz)
2
(ClO
4
)
2
and its deuterated version crystallizes
3.2 Bulk properties 39
in a monoclinic crystal structure, space group C2/m, with disordered ClO
4
(perchlorate)
anions. Below T = 163 K, the material undergoes a structural transition to the C2/c space
group (#15), with lattice parameters a = 14.045(5)

A, b = 9.759(3)

A, c = 9.800(3)

A and
= 96.491(4)
, which was determined by X-ray diraction [117].

The crystal structure is shown in Fig. 3.1(a-b). The Cu
2+
ions occupy 4e Wycko po-
sitions and pyrazine ligands link magnetic Cu
2+
ions into square-lattice planes lying in the
crystallographic bc-plane. The Cu
2+
-Cu
2+
nearest neighbor distances in the bc-plane are all
nearly identical and equal to 6.919(5)
A and 6.920(5)
A [117]. Tetrahedral perchlorate anions

located between the planes (Fig. 3.1(a)) provide a good spatial isolation of Cu
2+
pz layers
and substantially decrease the interlayer interactions. Thus, perfect square-lattices of copper
ions with a superexchange path mediated by pyrazine molecules are formed in the bc-plane,
as shown in Fig. 3.1(b).
3.2.2 Magnetic susceptibility
Magnetic susceptibility describes the magnetic response of a material to an applied magnetic
eld. Generally, the eld-induced magnetization is anisotropic and depends on the magnetic
eld direction. The susceptibility is thus not a scalar but a tensor of rank two:
ij
=
M
i
H
j
, (3.1)
where indexes j and i correspond to the directions of an applied eld and generated mag-
netization, respectively. We measured the magnetic susceptibility of Cu(pz)
2
(ClO
4
)
2
using
a commercial superconducting quantum interference device (SQUID) based magnetometer
produced by Quantum Design. A small rectangular single crystal of Cu(pz)
2
(ClO
4
)
2
with
mass m = 17.75(5) mg was loaded into the magnetometer with the applied eld parallel and
perpendicular to the bc-plane. The temperature dependence of the susceptibility measured
from T = 2 K to T = 50 K at
0
H = 1 T is shown in Fig 3.2.
The magnetic susceptibility along the crystallographic a direction is larger than in the
bc-plane. The sharp minimum in temperature dependence of susceptibility around T = 4 K
corresponds to the phase transition from the magnetic disorder towards the Neel long range
2
(ClO
4
)
2
Figure 3.1: (Color) (a) Three-dimensional view of the crystal structure of Cu(pz)
2
(ClO
4
)
2
.
The Cu
2+
ions are shown as big blue spheres and the C, N, Cl and O atoms as small green,
cherry, dark-blue and beige spheres, respectively. The D atoms are not shown for simplicity.
The yellow lines represent nearest neighbor Cu
2+
-Cu
2+
exchange paths in the square-lattice
plane lying in the bc plane. ClO
4
tetrahedra provide a good spatial isolation of the square-
lattice Cu layers along the a axis. (b) The projection of the crystal structure on the bc plane
shows the Cu
2+
square-lattice structure. The square lattice are shifted by (0, 0.5, 0) from one
square-lattice layer to the next. (c) Crystals of Cu(pz)
2
(ClO
4
)
2
grow naturally and have a
layered shape with a well dened crystallographic bc-plane.
antiferromagnetic phase.
Figure 3.2: The magnetic susceptibility
aa
,
bb
and
cc
of Cu(pz)
2
(ClO
4
)
2
measured as
function of temperature shown by red, blue and cyan circles, respectively.
The Curie-Weiss law for AFs for T > T
N
is
(T) =
C
T + T
N
, (3.2)
where C is the Curie constant of the sample and T
N
is the Neel temperature. The Curie
constant of material is equal to
C =
N(g
s
B
s)
2
k
B
, (3.3)
where N is the number of atoms in the sample, g
s
is Lande g-factor,
B
is the Bohr mag-
neton, s is the spin and k
B
is the Boltzmann constant. Thus, the magnetic susceptibility is
proportional to a squared g-factor. The g-factor values three orthogonal directions are equal
to g
b
= g
c
= 2.07(1) and g
a
= 2.27(1) as determined from the single crystal X-band electron
paramagnetic measurements [118]. The observed dierence of 19(1)% in the susceptibility
measured parallel and perpendicular to the bc-plane is thus in the good agreement with the
data obtained from X-band EPR, which predicts the dierence of 20.3(7)%. The dierence
in the magnetic susceptibility parallel and perpendicular to the Cu
2+
planes can thus be
explained by the dierent gyromagnetic factors. The nearly identical magnetic susceptibility
along the b- and c-direction suggest that spin anisotropies in the copper square lattice plane
2
(ClO
4
)
2
are small. The small dierence between
bb
and
cc
may be caused by a small misalignment
of the eld away from the bc-plane.
3.2.3 Specic heat
In order to obtain the HT phase diagram of Cu(pz)
2
(ClO
4
)
2
, we measured the specic heat as
a function of temperature for dierent magnetic eld strengths using the Physical Property
Measurement System by Quantum Design. A single crystal of deuterated Cu(pz)
2
(ClO
4
)
2
with mass m = 13 mg was xed on a sapphire chip calorimeter with Apiezon-N grease. The
measurements were done using the relaxation technique, which consists of the application
of a heat pulse to a sample and the subsequent tracking the induced temperature change.
The specic heat was obtained in the range from T = 2 K to T = 30 K in magnetic
elds of up to
0
H = 9 T, applied parallel and perpendicular to the copper square-lattice
planes. The measurements were done with the steps of T
1
= 0.05 K, T
2
= 0.2 K and
T
3
= 1 K in the temperature ranges T
1
= 2 6 K, T
2
= 6 8 K and T
3
= 8 30 K,
respectively. Care was taken to apply a small heat pulse of 0.1% of the temperature step
T and each measurement was repeated three times to increase accuracy. Specic heat of
Apiezon-N grease without Cu(pz)
2
(ClO
4
)
2
crystal was measured in the entire temperature
range separately and subtracted as a background from the total specic heat of the sample
and grease.
The temperature dependence of the specic heat of Cu(pz)
2
(ClO
4
)
2
is shown in Fig. 3.3(a,b)
for dierent magnetic elds applied perpendicular and parallel to the copper square-lattice
plane. At all elds, the temperature dependence of the specic heat reveals a well dened
cusp-like peak, indicating a second order phase transition towards 3D long-range magnetic
order. Previous zero-eld studies of Cu(pz)
2
(ClO
4
)
2
did not show an anomaly in the specic
heat [119]. Most likely, the high accuracy of our measurements played a crucial role in detect-
ing the zero-eld anomaly in the specic-heat curve. The small size of the ordering anomaly
is a consequence of the low dimensionality of the magnetism and an ordered magnetic mo-
ment that, due to quantum uctuations, is considerably smaller than the free-ion value. The
HT phase diagram assembled from the specic heat measurements is shown in Fig. 3.3(c).
The measurements show that the Neel temperature increases with increasing magnetic eld,
Figure 3.3: (Color) Specic heat of Cu(pz)
2
(ClO
4
)
2
as a function of temperature for dierent
magnetic elds applied parallel and perpendicular to the bc plane are shown in (a) and (b),
respectively. (c) The magnetic phase diagram obtained from the specic heat measurements.
from T
N
= 4.24(4) K at zero eld to T
K
= 5.59(3) K at
0
H = 9 T.
We also observe an increase of the specic heat with increasing magnetic eld in the
paramagnetic phase just above the 3D ordering temperature. We propose that the eld
dependence of the specic heat data is a consequence of eld-induced anisotropy in the
2D AF. In zero eld, a pure 2D Heisenberg AF orders at zero temperature, but quantum
Monte Carlo simulations [32] have shown that the application of an external eld induces an
Heisenberg-XY crossover and leads to a nite temperature Berezinskii-Kosterlitz-Thouless
transition T
BKT
[33, 34]. One consequence of this crossover is the increase of T
BKT
with
external eld for up to H < H
SAT
/4 and then a gradual decrease of the transition temperature
with increased elds. While the zero-eld 3D transition T
N
in Cu(pz)
2
(ClO
4
)
2
is driven by the
combination of 3D interaction and intrinsic XY anisotropy, the increase of T
N
as a function of
eld may thus be driven by an increase of the eective anisotropy and the associated increase
of T
BKT
. Similarly, we propose that the increase of the specic heat above the 3D ordering
temperature is caused by the eld-induced strengthening of a XY anisotropy: In the 2D AF on
2
(ClO
4
)
2
a square lattice, 2D topological spin-vortices appear above the Berezinskii-Kosterliz-Trousers
(BKT) transition as the preferable thermodynamic conguration. In applied magnetic eld
the vortices unbind above the BKT transition, leading to the increase of the specic heat
above the ordering temperature. The anisotropy crossover thus aects the specic heat in a
manner similar to the observed behavior [32].
Remarkably, the HT phase diagrams are identical for elds parallel and perpendicular to
the square-lattice planes. This suggests that the dominant exchange interactions between
nearest copper spins, J
1
, in bc-plane are close to the isotropic limit in spin space, in contrast
to with the strong spatial two-dimensionality of Cu(pz)
2
(ClO
4
)
2
.
3.3 Neutron diraction
3.3.1 Experimental details
To determine the ordered magnetic structure of Cu(pz)
2
(ClO
4
)
2
, we performed neutron
diraction experiments with powdered and single crystal samples. A powder diraction
experiment was performed using the cold-neutron powder diractometer DMC at the Paul
Scherrer Institute (PSI), Villigen, Switzerland. A diraction pattern was measured below and
above the Neel temperature using energy E = 4.637 meV. For the single crystal diraction
measurements, we used the cold-neutron three-axis spectrometer RITA2 at PSI, Villigen,
Switzerland. The HT phase diagram was also measured in this experiment. A crystal with
dimensions 771.5 mm and mass of m = 85 mg was wrapped into aluminum foil, xed with
wires on a sample holder and aligned with its reciprocal (0, k, l) plane in the horizontal scat-
tering plane of the neutron spectrometer. Data were collected at T = 2.3 K and T = 10 K in
magnetic elds up to
0
H = 13.5 T applied nearly perpendicular to the (0, k, l) plane using an
Oxford cryomagnet. Measurements were performed with the pyrolytic graphite (PG) (002)
Bragg reection as a monochromator. A cooled Be lter was installed before the analyzer
to suppress higher order neutron contamination for the nal energy E
i
= 5 meV. We also
used an experimental setup without Be lter, which allowed to use the second order neutrons
from the monochromator with E
i
= 20 meV, thus allowing to access to reections at high
wave-vector transfers.
3.3 Neutron diraction 45
Figure 3.4: The part of powder neutron diraction patterns measured at T = 1.5 K and at
T = 10 K are shown by blue and red lines, respectively.
Figure 3.5: (a) The scattering intensity at Q = (0, 1, 0) as function of rotation angle, mea-
sured at T = 2.3 K and at T = 10 K. The inset (b) shows the neutron scattering observed
at Q = (0, 0, 1) at the same temperatures.
2
(ClO
4
)
2
3.3.2 Magnetic order parameter
Fig. 3.4 shows the low-angle powder neutron diraction data obtained at T = 2 K and at
T = 10 K. The low-temperature data features a well-dened peak at 2 = 24.8
which is
not present at T=10K. This peak corresponds to Bragg diraction from a magnetic structure
modulated with either Q = (0, 1, 0) or Q = (0, 0, 1). Due to the small dierence between b and
c lattice constants ( 0.04
A), we can not distinguish these two wave-vectors. The magnetic

Bragg powder peaks are weak, due to the small size of the ordered magnetic moment, and
the powder pattern is insucient for the determination of the ordered magnetic structure.
Therefore it was necessary to perform a single crystal neutron diraction experiment.
Fig. 3.5 shows two magnetic peaks measured above and below the transition temperature
at Q = (0, 1, 0) and Q = (0, 0, 1) using a single crystal neutron diraction with nal energy
E
f
= 20 meV. This data directly demonstrates the presence of magnetic order below T
N
.
The magnetic Bragg peak widths are limited by the instrumental resolution, conrming that
the magnetic order is long-range.
The eld dependence of the magnetic scattering at Q = (0, 1, 0) measured using nal
energy E
f
= 5 meV reveals an increase of magnetic intensity as a function of eld from
zero to
0
H = 13.5 T as is shown in Fig. 3.6. The magnetic scattering was determined
by subtracting the non-magnetic background determined at T = 10 K. The increase of
magnetic diraction intensity with eld is most probably related to a quenching of quantum
uctuations by the magnetic eld, that simultaneously also leads to the observed increase of
the transition temperature T
N
. This result is in a good agreement with the specic heat data
indicating enhanced XY anisotropy in the applied magnetic eld. The intensity measured
at Q = (0, 1, 0) at T = 10 K as the function of applied eld did not reveal any magnetic
scattering, showing that magnetic elds do not lead to eld-induced antiferromagnetic order
in the paramagnetic phase. This is also evidence for the absence of o-diagonal terms in the
magnetic susceptibility tensor for elds along the a-axis.
The critical magnetic behavior was studied by measuring the peak intensity of the neutron
scattering at the antiferromagnetic wave vector Q = (0, 1, 0) and Q = (0, 3, 0) as function
of temperature in magnetic eld up to
0
H = 13.5 T. Typical scans are shown in Fig. 3.7.
The solid line shows that the increase of the antiferromagnetic intensity in the ordered phase
Figure 3.6: The magnetic peak intensity of neutron scattering at Q = (0, 1, 0) as function
of magnetic eld measured at T = 2.3 K. The non-magnetic scattering was estimated from
measurements at T = 10 K and subtracted from the overall peak intensity. The inset shows
the ordered antiferromagnetic moment as a function of eld.
Figure 3.7: (Color) (a) The temperature dependence of the neutron scattering peak intensity
measured at the antiferromagnetic point Q =(0, 1, 0). The data collected at
0
H = 0 T,
0
H = 2 T
0
H = 6 T and
0
H = 13.5 T are shown by circles, squares, triangles and
diamonds, respectively. The red lines are guides to the eye. The inset (b) represents the
peak intensity at Q = (0, 3, 0) as the function of temperature obtained at zero eld. T
N
was
found to be the same as for Q = (0, 1, 0).
2
(ClO
4
)
2
Figure 3.8: (Color) Neutron scattering peak intensity of Q = (0, 1, 0) as a function of tem-
perature and magnetic eld, applied perpendicular to the square-lattice planes. The results
obtained by specic heat measurements in magnetic eld applied parallel and perpendicu-
lar to the copper planes are shown by squares and circles, respectively. The neutron data,
measured for magnetic elds perpendicular to the copper planes, are shown by triangles.
close to T
N
is clearly steeper for high elds. The HT phase diagram compiled from the
temperature scans is shown in Fig. 3.8, conrming the phase diagram obtained from specic
heat measurements.
3.3.3 Ordered magnetic structure
The symmetry of the ordered magnetic phase was studied by single crystal neutron diraction.
Group theory was used to restrict the search only to magnetic structures that are allowed
by symmetry. The magnetic Bragg peaks at Q = (0, 1, 0) and Q = (0, 3, 0) indicate that the
magnetic structure breaks the C-centering of the chemical lattice and that Cu(pz)
2
(ClO
4
)
2
adopts an antiferromagnetic structure for T < T
N
. Symmetry analysis revealed six basis
vectors which belong to four irreducible representations and are listed in Tab. 4.5 (for details
see Appendix A).
The analysis is complicated by the fact that the single crystal probably consists of two
domains with interchanged b- and c-axis, which are nearly identical in length. A twinning
of the single-crystal in this manner is indicated by the observation of both the Q = (0, 2, 3)
and Q = (0, 3, 2) nuclear Bragg peaks with similar intensity, although Q = (0, 3, 2) is not
allowed for a C-centered lattice.
The experimental data are consistent with both
2
and
4
irreducible representations
listed in Tab. 4.4 and with two basis vectors

2
and

6
(see Appendix A). The ordered
magnetic structure of Cu(pz)
2
(ClO
4
)
2
can have magnetic moments aligned antiferromag-
netically either along crystallographic b- or c-axis as is shown in Fig. 3.9(a) and Fig. 3.9(b),
respectively. Due to a small number of observed magnetic reections and the crystallographic
twinning, our experiment cannot distinguish between these two magnetic structures.
The collinear spin arrangement in bc-plane is consistent with the absence of the Dzyaloshinsky-
Moriya interactions between NN. The spatial arrangement of the ordered magnetic moments
in adjacent square-lattice layers is ferro- and antiferromagnetic along ab- and ac-diagonal,
respectively. This is consistent with the chemical structure of Cu(pz)
2
(ClO
4
)
2
, where the
interlayer interaction pathway along ac-diagonal is shorter than the path along ab. The or-
dered magnetic structure of Cu(pz)
2
(ClO
4
)
2
with the preferable spin direction in bc-plane is
consistent with recent ESR measurements [120] which showed a presence of a small energy
gap E
ig
0.01 meV at the antiferromagnetic zone center, Q = (0, 1, 0). Most probably this
gap is induced by a small Ising-like anisotropy. The resolution of the neutron spectrometer,
which we used to measure the spin gap at Q = (0, 0, 1), was equal to
En
0.1 meV and
therefore it did not allow us to observe E
ig
. Due to a small energy scale of E
ig
compared to
the dominant exchange interactions between spins in the system, we neglect the presence of a
possible Ising-like anisotropy in further discussions of the spin dynamics in Cu(pz)
2
(ClO
4
)
2
.
The measured Bragg peak intensities were corrected for the instrumental resolution func-
tion. The value of the ordered magnetic moment was obtained from a minimization of
= [R
calc
R
exp
[, where R
exp
is the measured ratio of the magnetic Bragg peak intensity
to the nuclear Bragg peak intensity, R
calc
= [F(Q)
magn
[
2
/[F(Q)
nucl
[
2
, F(Q)
magn
and F(Q)
nucl
are the magnetic and nuclear form factors, respectively. The t was performed for two mag-
netic peaks observed at Q = (0, 1, 0) and Q = (0, 3, 0) and two nuclear peaks measured at
Q = (0, 2, 4) and Q = (0, 0, 6). The value of the ordered magnetic moment in zero eld,
which was obtained in this way, is m
0
= 0.47(5)
B
. The comparison of R
calc
and R
exp
for
2
(ClO
4
)
2
Figure 3.9: Two possible magnetic structures of Cu(pz)
2
(ClO
4
)
2
belonging to the
2
and
4
irreducible representations (see Tab. 4.4), are shown in (a) and (b), respectively. Two
adjacent square-lattice Cu
2+
layers, separated by a (0.5,0.5,0) lattice unit translation, are
depicted by open and lled arrows. Cu
2+
Cu
2+
interlayer interaction pathway along ac
diagonal corresponds to the vertical distance between lled and open symbols in (a) and (b).
two magnetic and two nuclear Bragg peaks is presented in the Tab. 3.1. The calculated value
|F(0,1,0)|
2
|F(0,2,4)|
2
|F(0,1,0)|
2
|F(0,0,6)|
2
|F(0,3,0)|
2
|F(0,2,4)|
2
|F(0,3,0)|
2
|F(0,0,6)|
2
R
exp
10
4
3.72(7) 5.13(12) 1.89(18) 2.60(25)
R
calc
10
4
4.35 4.57 2.16 2.26
Table 3.1: The measured and the calculated ratios of squared magnetic to nuclear structure
factors for dierent Bragg peaks. The calculated values were obtained from a minimization
of = [R
calc
R
exp
[ and correspond to the ordered magnetic moment m
0
= 0.47
B
.
of the ordered magnetic moment is smaller than the free-ion magnetic moment, indicating
the presence of strong quantum uctuations in the magnetic ground state of Cu(pz)
2
(ClO
4
)
2
.
The inset in Fig. 3.6 shows the increase of the ordered antiferromagnetic moment from
m
0
= 0.47(5)
B
in zero eld to m
0
= 0.93(5)
B
in
0
H = 13.5 T. This is direct evidence for
the suppression of quantum uctuations by the applied magnetic eld due to induced XY
anisotropy as suggested by our specic heat measurements.
3.4 Neutron spectroscopy
3.4.1 Experimental details
We measured the spin dynamics in the antiferromagnetically ordered phase of Cu(pz)
2
(ClO
4
)
2
in zero and applied magnetic elds using neutron spectroscopy. In total, three experiments
were performed. Two experiments were performed using the cold-neutron three-axis spec-
trometer PANDA at FRM-2, Garching, Germany. One experiment was performed using the
cold-neutron triple-axis spectrometers IN14 at ILL at Grenoble, France.
The zero eld studies using PANDA were performed on two single crystals with a total
mass of m = 1 g which were wrapped into aluminum foil, xed on a sample holder with wires
and co-aligned in an array with a nal mosaic spread of 1
. The reciprocal (0, k, l) plane of

the sample was aligned in the horizontal scattering plane of the neutron spectrometer. These
measurements were performed in zero magnetic eld and at temperature T = 1.42 K using
a
4
He cryostat generally referred to as an Orange cryostat. The nal energy was either set
to E
f
= 4.66 meV or E
f
= 2.81 meV using a PG(002) analyzer. Data were collected using a
PG(002) monochromator and a cooled Be lter installed before the analyzer.
The neutron experiments in applied magnetic elds were performed using an array of
deuterated Cu(pz)
2
(ClO
4
)
2
single crystals with a total mass up to 2g co-aligned with a mosaic
of 0.5
. The sample was aligned with its reciprocal (0, k, l) plane in the horizontal scattering
plane. A cryomagnet allowed the application of vertical magnetic elds up to
B
H = 14.9 T.
The magnetic eld was thus nearly perpendicular to the square-lattice planes. To probe
the ground state as a function of magnetic eld, we used a dilution refrigerator, reaching
temperatures of the order of 50 mK in each of the two experiments. The measurements were
performed using a xed nal energy E
f
= 4.66 meV and E
f
= 2.98 meV for the PANDA
and IN14 experiments, respectively, obtained via the (002) Bragg reection from a pyrolithic
graphite (PG) monochromator, a focused analyzer and a cooled Be lter before the analyzer.
3.4.2 Spin dynamics in zero eld
Constant energy scans were performed near the antiferromagnetic zone centers Q = (0, 0, 1)
and Q = (0, 1, 0) for energy transfer E in the range from E = 0.5 meV to E = 3 meV
2
(ClO
4
)
2
Figure 3.10: (Color online) A series of constant energy scans performed along the (0, k,
1) and (0, -1, l) directions at dierent energy transfers E in zero magnetic eld and at
T = 1.42 K. Please note the changing scale of the vertical axis for the dierent scans. The
solid lines correspond to a convolution of two Gaussians with the resolution function.
and are shown in Fig. 3.10. The observed magnetic peaks are resolution limited, indicating
that these magnetic excitations are long-lived magnons associated with a long-range ordered
magnetic structure.
Constant wave-vector scans were performed at the antiferromagnetic zone centers in the
energy transfer range from E = 0 meV to E = 0.7 meV (Fig. 3.11(a), b). These scans
reveal a magnetic mode which is gapped and has a nite energy E
zc
= 0.201(8) meV at
the antiferromagnetic zone center. The energy gap at the antiferromagnetic zone center is
attributed to the presence of a small XY anisotropy in the nearest-neighbor two-ion exchange
interactions, because a single-ion anisotropy of type D(S
z
)
2
is not allowed for S = 1/2.
Constant wave-vector scans away from the antiferromagnetic zone center carried out
at higher energies are shown in Fig. 3.11(c). The energies of the magnetic excitation at
the symmetrically identical antiferromagnetic zone boundary points Q
zb1
= (0, 0.5, 1) and
Q
zb2
= (0, 0.5, 1) are equal to E
zb1
= 3.629(6) meV and E
zb2
= 3.599(13) meV, respec-
tively. The peaks observed in the constant wave-vector scans at Q
zb1
and Q
zb2
are resolution
limited. This experimental observation together with the identity of the values E
zb1
and E
zb2
conrms the NN interactions in bc-plane are identical along the square-lattice directions. In
case of dierent strengths for the NN interactions in the bc-plane, a broadening of the mag-
netic excitations at Q
zb1
and Q
zb2
would be observed or every energy scan would show two
peaks. The observed one-magnon mode can thus qualitatively be explained by the 2D spin
Hamiltonian with NN exchange interactions:
H
NN
=
i,j
J
z
1
S
z
i
S
z
j
+ J
xy
1
(S
x
i
S
x
j
+S
y
i
S
y
j
), (3.4)
where i, j indicates the sum over NN in the bc-plane, J
z
1
and J
xy
1
are z-, xy-components of
the NN interactions, respectively.
We also studied the spin-wave dynamics along the antiferromagnetic zone boundary by
performing constant wave-vector scans along the Q = (0, 0.5, l) direction from l = 1 to
l = 2. Typical data are shown in Fig. 3.13(a-c) and the observed zone boundary dispersion
is shown in Fig. 3.13(d). The onset of the scattering at Q = (0, 0.5, 1.5) is reduced by
10.7(4)% in energy compared to Q = (0, 0.5, 1). The decrease of the resonant mode energy
at Q = (0, 0.5, 1.5) results from a resonating valence bond quantum uctuations between NN
spins [13, 110].
In order to subtract a nonmagnetic contribution from the background in the energy scan
at Q = (0, 0.5, 1.5) we performed measurements with the sample turned away from magnetic
scattering. The background-subtracted data are shown in Fig. 3.13(a). The width of the
scattering peak as a function of energy at Q = (0, 0.5, 1.5) is clearly broader than the in-
strumental resolution. This implies the existence of a magnetic continuum scattering in this
region of the antiferromagnetic zone boundary. This non-trivial magnetic continuum and the
dispersion at the zone-boundary result from quantum uctuations in Cu(pz)
2
(ClO
4
)
2
. The
observed dispersion at the zone boundary is slightly larger than expected from series expan-
2
(ClO
4
)
2
Figure 3.11: (Color) The constant Q-scans collected at small energy transfer show the energy
of a gapped spin-wave at the antiferromagnetic zone center performed at Q = (0, 0, 1) and
at Q = (0, 1, 0) are presented in (a) and (b), respectively. (c) Constant Q-scans performed
close to the antiferromagnetic zone boundary at high energy transfer show the dispersion of
the spin-wave. The measurements were performed in zero magnetic eld and at T = 1.42 K.
The solid lines represent the convolution of a Gaussian with the resolution function.
sion calculations and Quantum Monte Carlo simulations for 2D Heisenberg square-lattice
AF with NN interactions [13, 11]. Our collaborators developed series expansion calculations
for the J
1
J
2
model [124, 125, 126] and their result shows that the addition of J
2
leads
to an enhancement of the zone boundary dispersion (see section 3.4.3 for details). Thus for
Cu(pz)
2
(ClO
4
)
2
the increased zone-boundary dispersion is attributed to a small AF NNN
interaction of the order of J
2
0.02 0.05J
1
.
We performed the spin-wave calculations in linear approximation based on the following
Hamiltonian:
H =

H
NN
+ J
2
i,k
S
i
S
k
, (3.5)
where

H
NN
is given by eq. 3.4, i, k is the sum over NNN in the bc-plane and J
2
is the NNN
exchange interaction. The linear spin wave theory (for details see Appendix B) yields two
spin-wave modes with the dispersion
h
q
=
_
A
2
q
B
2
q
, (3.6)
where
A
q
= 4SJ
xy
1
+ S(J
xy
1
J
z
1
)(cos(qb) + cos(qc)) 4SJ
2
+ 4SJ
2
(cos(qb) cos(qc)),
B
q
= S(J
xy
1
+ J
z
1
)(cos(qb) + cos(qc)). (3.7)
This implies that the exchange anisotropy mostly aects the magnon energy close to the
antiferromagnetic zone center, while the zone boundary energy remains nearly unaected by
the exchange anisotropy. In the 2D S = 1/2 AF, the energy of a classical (large-S) spin-
wave mode is renormalized due to quantum uctuations with the best theoretically predicted
renormalization factor Z
c
= 1.18 [15, 12]. Therefore the energy at the antiferromagnetic zone
boundary is equal to E
zb
= 2(Z
c
J
z
1
J
R
2
), where J
R
2
is the renormalized NNN interaction.
The calculated xy-component of NN and NNN exchange interactions are equal to J
xy
1
=
1.563(13) meV and J
2
0.02J
xy
1
(see section 3.4.3), respectively. According to the linear
spin wave theory E
2
zc
= 8J
xy
1
(J
xy
1
J
z
1
) and thus J
z
1
= 0.9979(2)J
xy
1
.
The values of the xy- and z-components of the NN interaction obtained from our neutron
measurements are in a good agreement with the result of magnetic susceptibility measure-
ments [121], which yielded J
xy
1
= 1.507(26) meV and J
z
1
= 0.9954 J
xy
1
. The small XY
anisotropy indicates that the dominant exchange interaction between nearest copper ions
in the bc-plane in Cu(pz)
2
(ClO
4
)
2
, while spatially very anisotropic, is close to the isotropic
limit in spin space, explaining the strong similarity of the HT phase diagrams measured in
magnetic elds applied parallel and perpendicular to copper square-lattice (Fig. 3.8).
The inelastic-scattering data were tted with the Gaussian instrumental resolution func-
tion convoluted numerically with the model Hamiltonian (3.5). The result of the ts is shown
by the red lines in Fig. 3.10 and Fig. 3.11, and provides a good description of the observed
spin waves. The color plot of the neutron scattering intensity, which is shown in Fig. 3.12,
summarizes the observed magnetic excitations in both crystallographic directions. The black
lines display the result of the linear spin wave theory, showing that the observed dispersive
2
(ClO
4
)
2
Figure 3.12: (Color) Color plot of the scattering intensity, showing the dispersion along the
Q = (0, 1, l) and Q = (0, k, 1) directions measured at zero eld, presented in the left and
right panels, respectively. The color plots were obtained by merging a total of ve and
thirteen constant wave-vector scans. The solid line represents the dispersion computed from
linear spin wave theory using J
xy
1
= 1.563 meV, J
z
1
= 0.9979J
xy
1
and NNN exchange equal to
J
2
= 0.02J
xy
1
as described in the text.
excitation is well characterized by the Hamiltonian (3.5).
The measured spin wave dispersion is similar to that observed in another 2D square-
lattice antiferromagnetic material, namely copper deuteroformate tetradeuterate (CFTD),
where the exchange interaction strength is equal to J = 6.3(3) meV and the energy gap of
E = 0.38(2)meV is present at the antiferromagnetic zone center. However, the energy gap in
CFTD is induced by the presence of small antisymmetric Dzyaloshinsky-Moriya interaction
D = 0.0051(5) meV between NN [105, 106]. Another example with comparable properties is
K
2
V
3
O
8
with 2D NN exchange strength J = 1.08(3) meV and small energy gap at antiferro-
magnetic point equal to E = 0.072(9) meV [109], which is described by Dzyaloshinsky-Moriya
and easy-axis anisotropies [122]. In contrast, Dzyaloshinsky-Moriya interactions between NN
in Cu(pz)
2
(ClO
4
)
2
are forbidden by symmetry (see Sec. 4.4) and the energy gap at the anti-
Figure 3.13: (Color) (a) The energy scan at Q = (0, 0.5, 1.5) with the background subtracted
as explained in the text. The energy scans performed at wave-vectors Q = (0, 0.5, 1.7) and
Q = (0, 0.5, 2) are shown in (b) and (c), respectively. The red curves are ts of a Gaussian
function convoluted with the resolution function. (d) The antiferromagnetic zone boundary
dispersion measured in zero magnetic eld and at T = 1.42 K.
2
(ClO
4
)
2
ferromagnetic zone center is generated by small XY exchange anisotropy.
3.4.3 Spin dynamics in applied magnetic elds
A color plot of the normalized neutron scattering spectra at the antiferromagnetic zone
boundary is shown in Fig. 3.14 for zero applied eld and
0
H = 14.9 T. These data were
measured using the IN14 spectrometer. At zero eld, the onset of scattering at reciprocal
wave-vector Q = (0, 0.5, 1.5) is reduced by 11.5(7)% in energy compared to Q = (0, 0.5, 2),
at odds with spin-wave theory. However, this result is consistent with our independent
investigation of Cu(pz)
2
(ClO
4
)
2
using PANDA spectrometer (see Sec. 3.4.2). The observed
zone-boundary dispersion is larger than expected from Quantum Monte Carlo simulations
and series expansion calculations for the Heisenberg square-lattice AF with nearest-neighbor
interactions, which predict a zone-boundary dispersion of 8% to 10% [13, 11]. Our observation
is opposite to what has been observed in the high-T
c
material La
2
CuO
4
where the energy
at Q = (0, 0.5, 1.5) is higher than at Q = (0, 0.5, 2) [111]. The latter has been attributed to
ring-exchanges arising from nite-U/t [123].
The single-magnon energies were computed for dierent relative strengths J
2
/J
1
for zero
and
0
H = 14.9 T by our collaborators using series expansion calculations. The comparison
of the numerical calculations shown in Fig. 3.15 and our experimental data (see Fig. 3.14)
indicates that the zone-boundary dispersion is increased due to a small AF next-nearest
neighbor interaction of the order of J
2
0.02 0.05J
1
.
According to spin wave theory, the energy at Q = (0, 0.5, 2) is equal to E
(0,0.5,2)
= 2(J
1
J
2
) at all elds. Next-nearest neighbor interactions thus lead to a smaller zone-boundary
energy, and thus to a smaller eective nearest-neighbor exchange J. Using J = J
1
J
2
and J = 1.53(8) meV determined from susceptibility measurements [119, 127], the eld-
induced change of E
(0,0.5,2)
is obtained from the eld dependence of the renormalization factor
Z
c
= E
(0,0.5,2)
/2J, yielding Z
c
= 1.19(2) at zero eld in excellent agreement the predicted
value of Z
c
= 1.18 [13].
Fig. 3.16(a) shows that the spin excitation at Q = (0, 0.5, 1.5) is considerably broader
than experimental resolution, and that neutron scattering extends to about E = 3.9 meV.
This represents clear experimental evidence of a magnetic continuum at Q = (0, 0.5, 1.5)
Figure 3.14: Zone boundary spin dispersion at zero eld and
0
H J. Color plot of the
normalized scattering intensity I(Q, ) at T = 80 mK, showing the dispersion from Q =
(0, 0.5, 1.5) to Q = (0, 0.5, 2) at zero eld and
0
H = 14.9 T under otherwise identical
conditions. Both panels present smoothed data obtained by performing six constant Q-scans
from Q = (0, 0.5, 2) to Q = (0, 0.5, 1.5) with a 0.05 meV energy step.
2
(ClO
4
)
2
Figure 3.15: Series expansion calculations of the zone-boundary dispersion. Theoretical
magnon dispersion for dierent values of the next-nearest neighbor exchange interaction J
2
in zero magnetic eld (left panel) and in a
0
H = 14.9 T magnetic eld (right panel). The
value of the nearest neighbor interaction J has been normalized to t the experimental data.
The normalization constants are shown in the legend [128].
of the square-lattice AF that is not expected from spin-wave theory. The continuum is
clearly stronger than in copper deuteroformate tetradeuterate (CFDT) where next-nearest
neighbor exchange are absent [110], suggesting that next-nearest neighbor exchange enhances
continuum excitations in the 2D S = 1/2 square-lattice AF. The extended continuum in
Cu(pz)
2
(ClO
4
)
2
is also in contrast to well-dened excitations observed in La
2
CuO
4
near
Q = (0, 0.5, 1.5), suggesting that ring exchange has the opposite eect on the continuum to
next-nearest neighbor interactions. Further, Fig. 3.14 also provides evidence of an energy
gap around Q = (0, 0.5, 2) that separates a main mode and a much weaker continuum above
4.2 meV, as predicted by Ho et al. [14].
Fig. 3.16(c) shows that magnetic elds strongly aects the quantum uctuations at the
zone boundary: The energy of the magnetic excitation at Q = (0, 0.5, 2) decreases much faster
with eld than that at Q = (0, 0.5, 1.5). The zone-boundary dispersion at
0
H = 14.9 T
is inverted from what it was at zero eld. The series expansion calculations show that,
with the application of a magnetic eld, the inversion of the zone boundary dispersion only
occurs for suciently small J
2
/J
1
. A ve percent J
2
/J
1
no longer shows the reversal of the
dispersion that is seen in our experiments. This implies that even a relatively small next-
Figure 3.16: Field dependence of zone-boundary excitations. Energy scans at Q = (0, 0.5, 1.5)
and Q = (0, 0.5, 2) are shown in (a) and (b), respectively. The data was measured at T =
80 mK. The black solid line in (b) represents linear spin-wave excitations convoluted with the
resolution function. Apart from the continuum region, all the experimentally measured peaks
are resolution limited. The eld dependent onset of magnetic scattering at Q = (0, 0.5, 1.5)
and Q = (0, 0.5, 2) as a function of energy is shown in (c) by red triangles and black circles
respectively. The dashed red and black lines represent the estimate from the series expansion
calculations with J
1
= 1.54 meV and J
2
= 0.02J
1
.
2
(ClO
4
)
2
nearest neighbor interaction is eective in enhancing the continuum of excitations, consistent
with the estimate that J
2
/J
1
= 0.02. The quantum renormalization factor Z
c
decreases
rapidly from Z
c
= 1.19(2) at zero eld and approaches Z
c
= 0.99(2) at
0
H = 14.9 T, also
consistent with the calculations.
It is known that the wave-vector dependence of the magnetic excitations at the zone
boundary is a result of resonating valence bond quantum uctuations between nearest-
neighbor spins that reduce the energy of resonant excitations near Q = (0, 0.5, 1.5) below
what is expected from renormalized spin-wave theory [13, 110]. The eld-induced reversal
of the zone-boundary dispersion reveals that magnetic elds of the order of H J strongly
couple to these local quantum uctuations. This dispersion, that is not expected from spin-
wave theory, demonstrates the presence of local quantum uctuations in the 2D S = 1/2
square-lattice AF even for elds of the order of H J. The quantum origin of the disper-
sion reversal is also conrmed by the series expansion calculations. The observed dispersion
suggests that the energy of the magnetic resonance at Q = (0, 0.5, 1.5) is raised by 4.5(7)%
above that of the renormalized spin-wave theory, providing direct evidence of a eld-tuned
resonating valence bond uctuations.
The excitation spectrum at
0
H = 12 T features two well dened magnetic modes of
excitations (Fig. 3.17). The spectrum consists of a Goldstone mode, that indicates unbroken
rotational spin symmetry in the plane perpendicular to the magnetic eld, and a gapped
mode. The eld dependence of the mass of the gapped mode at the AF zone center, shown
in Fig. 3.18, is linear, which is consistent with the theoretical arguments discussed in [129].
The nite gap at zero eld, obtained by the linear t to the experimental data, implies the
existence of a small XY exchange anisotropy in the system and it is described by a small
anisotropic NN exchange interaction J
z
1
= 0.9979(2)J
xy
1
(see sec. 3.4.2). We also analyzed
the spectral weight of the gapped excitation at Q = (0, 0, 1). Our calculations completely
describe the observed eld dependence of the peak intensities of the gapped mode at the AF
zone center (Fig. 3.18(c)).
Fig. 3.17 shows the observed dispersion from Q = (0, 1, 0) to Q = (0, 1, 0.5) compared
to linear spin-wave theory. The linear spin-wave theory calculations in a magnetic eld are
Figure 3.17: Spin dispersion for
0
H J. (a) The spin wave dispersion in Cu(pz)
2
(ClO
4
)
2
measured at
0
H = 12 T and T = 80 mK. The red line represents the spin-wave dispersion
with J
1
= 1.54 meV and J
2
= 0.02J
1
. (b,c) Energy scans at Q = (0, 10.4), Q = (0, 10.3)
provide evidence of a mode with a eld-induced gap. (d) Constant-energy scattering at
1 meV energy transfer provide evidence for the Goldstone mode. The solid line in (b)-(d)
corresponds to a convolution of a Gaussian with the resolution function, demonstrating that
the excitations are resolution limited.
2
(ClO
4
)
2
Figure 3.18: Field dependence of the zone-center excitation. Energy scans performed at
Q = (0, 0, 1) at
0
H = 2 T,
0
H = 6 T,
0
H = 10 T (a) and the gap energy at the AF point
plotted as the function of eld (b). The data was measured at T = 80 mK. The solid lines
in (a) are the ts of a Gaussian function convoluted with the resolution function. The lled
circles in (b) represent the experimental data. The solid line in (b) is the linear t of the gap
energy. Black circles in inset (c) show the measured intensities as function of magnetic eld
and the curve is the scattering intensity calculated using linear spin-wave theory.
performed for the following Hamiltonian:
H =

H
NN
+ J
2
<i,k>
S
i
S
k
0
H
i
S
a
i
, (3.8)
where

H
NN
is dened in eq. 3.4, i, k next nearest neighbor pairs and S
a
is a spin component
perpendicular to the bc plane. The renormalized spin wave theory with J
e
= 1.54(1)meV
and Z
c
= 1.03(1) for
0
H = 12 T describes qualitatively the observed dispersion, as shown
in Fig 3.17(a), but there are clear dierences that may reect the importance of magnon-
magnon interactions [35, 36]. Possibly, better agreement could be obtained by including
higher-order terms in the spin-wave calculation.
3.5 Summary 65
3.5 Summary
In summary, our comprehensive experimental investigation of Cu(pz)
2
(ClO
4
)
2
shows that this
material is the rst weakly frustrated 2D S = 1/2 AF on a square lattice with an absence of
Dzyaloshinsky-Moriya interaction between NN. We show that the zone-boundary dispersion
and the zone-boundary continuum of the 2D S = 1/2 square-lattice AF are enhanced by
NNN interactions, while the spin-wave energies merely experience a small renormalization.
Magnetic elds of the order of H J lead to a qualitative change of the quantum uctu-
ations that suppress the continuum of excitations and renormalize the spin-wave velocity,
but without suppressing the zone-boundary dispersion that arises from non-trivial quantum
uctuations. In fact, we nd that the zone-boundary dispersion is inverted compared to
zero eld, providing direct evidence of a eld-induced change of resonating valence bond
uctuations.
2
(ClO
4
)
2
Chapter 4
Magnetism in quasi-one-dimensional
S = 1 antiferromagnet NiCl
2
4SC(NH
2
)
2
4.1 Introduction
Organo-metallic material dichlorotetrakisthiourea-nickel (II) NiCl
2
4SC(NH
2
)
2
, also known
as DTN, consists of Ni
2+
ions located in the corners and the centers of the chemical tetragonal
body-centered unit cell [130]. The exchange interaction between neighbor spins S = 1 are
equal to J
c
1.64(3) K and J
ab
0.16(1) K along the crystallographic c-axis and in the
ab-plane, respectively [131]. Because of strongly interacting spins along the tetragonal c-axis,
DTN can be viewed as a system of weakly coupled S = 1 chains.
Due to a presence of a large single-ion XY-anisotropy D 8 K, a singlet ground state
S
z
= 0 at zero magnetic eld is separated by an energy gap from the excited doublet S
z
= 1
[131, 132, 133] and the correlations between spins remain short-range in the zero-temperature
limit. At zero temperature, a magnetic eld applied along the crystallographic c-axis splits
the excited doublet and mixes its lower member with the ground state at the rst critical eld,
H
c1
, leading to 3D long-range antiferromagnetic order with preserved U(1) symmetry. The
predicted order of the antiferromagnetic phase has transverse spin components, perpendicular
to the applied eld and aligned antiparallel between nearest neighbors in the crystallographic
ab-plane. The eld-induced QPT from a paramagnetic to a 3D antiferromagnetic phase can
be treated as BEC of magnons in DTN.
2
4SC(NH
2
)
2
The eld-induced magnetic order and the eld-temperature phase diagram of DTN had
been studied previously by several techniques. Magnetization measurements were performed
in magnetic elds up to
0
H = 18 T at dierent temperatures [132, 133]. The gyromagnetic
Lande factor is equal to g
= 2.26, g
= 2.34 parallel and perpendicular to the tetragonal

axis, respectively. The transitions from the quantum paramagnetic to the 3D long-range
antiferromagnetic state and from antiferromagnetic to a fully polarized ferromagnetic state
occur in the zero-temperature limit at the rst and the second critical elds, which are
equal to
0
H
c1
= 2.1 T and
0
H
c2
= 12.6 T, respectively [134]. Based on the temperature
dependence of the critical elds, the critical exponent of this QPT was determined from the
power law H
c
(T) H
c
(0) T
using specic heat and magnetocaloric eect measurements

by Zapf and collaborators [131]. Using the extrapolation method [69], it was found to be
equal to = 1.5 as predicted for BEC. The QCP corresponding to H
c1
thus belongs to the
universality class of the dilute Bose gas, with an eective dimensionality d = 2.
The magnetostriction eect was measured in magnetic elds applied parallel (H | c) and
perpendicular (H c) to the tetragonal axis of DTN [134, 135]. A eld-induced contraction
of the c-axis was observed in magnetic elds H
c1
< H < 6 T for H | c. Higher magnetic
elds, 6 T < H < H
c2
, lead to an expansion of the tetragonal axis. This can be understood
as following: The magnetic system increases its antiferromagnetic exchange interaction J
c
by contraction of the c-axis minimizing the magnetic energy. Due to a eld-induced canting
of magnetic moments towards the eld direction, the NN are increasingly aligned ferromag-
netically above
0
H 6 T. In order to minimize the magnetic energy associated with the
ferromagnetic coupling, the system thus expands the tetragonal axis in order to reduce the
antiferromagnetic exchange. These magnetostriction measurements also showed that the an-
tiferromagnetic phase between H
c1
and H
c2
shrinks as a function of angle between the
magnetic eld and the c-axis, collapsing near the critical angle = 55
. No magnetic order
was observed for magnetic elds applied in the ab-plane.
Systematic studies of the magnetic excitations in DTN using electron spin resonance
(ESR) technique were performed by Zvyagin et al [136, 137]. The observed modes are shown
as a function of applied eld in Fig. 4.1. At T = 1.6 K, ESR measurements revealed the
modes A and C, whose energies extrapolate to a low energies towards 7.7 T. Upon
4.1 Introduction 69
Figure 4.1: The frequency-eld dependence of ESR in DTN measured at T = 1.4 K is shown
by open circles and at T = 0.45 K are shown by squares and stars (Ref. [137]). Grey circles
represents the data obtained at T = 1.6 K. The dashed red and solid cyan lines show results
of calculations for the simplest axially symmetric two-sublattice antiferromagnetic model and
results of model calculations assuming small Dzyaloshinsky-Moriya interactions, respectively.
The gure is taken from the original publication by Zvyagin et al [136].
cooling, these two modes develop into two modes K and L that are separated by a nite
energy. The observation of the gapped mode L and the splitting of mode K in applied
magnetic elds 6 T < H < 10 T indicates the presence of additional interactions that are
not included in the simple axially symmetric two-sublattice antiferromagnetic model. The
authors explained their experimental data by Dzyaloshinsky-Moriya interactions. However,
such the interactions are forbidden by the symmetry of DTN and thus cannot explain the
observed gapped modes.
In this chapter, we present the results of neutron diraction and neutron spectroscopy
measurements performed on single crystals of DTN. We determined the ordered magnetic
structure in the eld-induced AF phase, which is collinear antiferromagnetic order between
nearest-neighbors perpendicular to the applied eld. The value of the ordered magnetic
moment as a function of magnetic eld and temperature is estimated from neutron dirac-
tion. We also determine the magnetic phase diagram as a function of magnetic eld and
temperature as well as a function of the angle between applied eld and the tetragonal axis.
Using neutron spectroscopy, the energy of the excited doublet at the antiferromagnetic
zone center is investigated as a function of magnetic eld. We demonstrate that DNT un-
2
4SC(NH
2
)
2
dergoes a BEC of magnons at the rst critical eld H
c1
. In order to determine the spin
Hamiltonian including the strength of the NNN exchange interaction between corner and
center in the chemical unit cell, we measured the one-magnon dispersion in the fully magne-
tized phase of DTN. The excitation spectrum deep in the antiferromagnetic phase is complex
and gives evidence of magnetic interactions not present in the zero-eld or high-eld limit.
We interpret this as a consequence of a coupling of the magnetic structure to the chemical
lattice that leads to additional interactions in the antiferromagnetic phase.
4.2 Experimental details
The ordered magnetic structure and magnetic eld-temperature (HT) phase diagram with
magnetic elds applied parallel to the crystallographic c-axis were studied using the thermal
neutron two-axis diractometer D23 located at ILL, Grenoble, France. A single crystal of
deuterated DTN with dimensions 5 5 7 mm was aligned with its reciprocal (h, k, 0) plane
in the horizontal scattering plane of the neutron diractometer and loaded into a dilution
refrigerator. Magnetic elds up to
0
H = 12 T were applied along the tetragonal axis. Data
were collected using neutrons with a wave length = 1.279

A selected by a pyrolytic graphite
(PG) (002) Bragg reection. Using a lifting detector which can cover a symmetric angular
range 30
, it was possible to access Bragg reections located away of the (h, k, 0) plane. In
order to determine the eld-induced magnetic order, a total of 124 nuclear and 23 magnetic
Bragg peaks were measured at
0
H = 6 T.
The spin dynamics in the fully magnetized phase of DTN was investigated at the Swiss
Spallation Neutron Source, using the cold-neutron three-axis spectrometer RITA2. The
sample was mounted in the same way as in the D23 experiment and loaded into dilution insert.
To reach the fully magnetized phases, we used a 15 T split-coil magnet and performed the
measurements at
0
H = 13.3 T. The crystal was aligned with its reciprocal (h, k, 0) plane in
the horizontal scattering plane of the spectrometer and the magnetic eld was applied along
the c-axis. The dispersion of the low-lying excitation was mapped out through constant
wave-vector scans using neutrons scattered and focused by PG(002) monochromator nal
wave length of E
f
= 4.7 meV.
4.2 Experimental details 71
Figure 4.2: (a) Three-dimensional view of the
crystal structure of DTN. The nickel and chlo-
rine atoms are shown as green and cherry
spheres, respectively. All other atoms are not
shown for a simplicity. (b) Single crystals of
NiCl
2
4SC(NH
2
)
2
The dependence of the magnetic phase
diagram on the angle between applied eld
and the crystallographic c-axis was mea-
sured using the two-axis neutron dirac-
tometer E4 at HMI, Berlin, Germany. Four
single crystals of deuterated DTN with di-
mensions 5 5 10 mm were co-aligned
with a mosaic spread less than 1
. The sam-
ple was loaded into a horizontal eld mag-
net and aligned with its reciprocal (h, h, l)
plane in the horizontal scattering plane of
the instrument. PG crystals bent verti-
cally were used as the focusing monochro-
mator for the wave length lambda = 2.44

A.
Scattered intensities were observed using a
two-dimensional position-sensitive detector.
The experiment was performed using a di-
lution refrigerator, at temperatures below
T = 0.8 K.
The wave-vector and eld dependence of
the spin doublet was studied using FLEX
in magnetic eld up to
0
H = 6 T. We used the same sample mount with four co-aligned
crystals, a horizontal eld magnet and a dilution refrigerator as in the E4 diraction ex-
periment. FLEX is a triple-axis spectrometer for cold neutrons located at HMI, Berlin,
Germany. PG(002) reections were used as monochromator and neutrons with nal wave
length of = 5.236

A or = 4.833

A were detected. A collimation of 60 located after the
monochromator and a cooled beryllium lter installed before the analyzer were used to sup-
press the beam divergence and higher order neutron contamination. The sample was loaded
into a horizontal eld magnet and aligned with its reciprocal (h, h, l) plane in the horizontal
scattering plane of the instrument.
2
4SC(NH
2
)
2
In order to illustrate a eld-induced BEC of magnons and measure the magnetic phase
diagram as a function of the angle between an applied eld and the crystallographic c-axis,
we had to use a horizontal eld magnet. This necessity was imposed by the following: DTN
undergoes a eld-induced order only in a eld applied close to the tetragonal axis and the
magnetic ordering vector in the antiferromagnetic phase is equal to k = (0.5, 0.5, 0.5) (see
Sec. 4.3.1). This implies that the scattering plane of the neutron spectrometer has to be
located close to the direction of the applied magnetic eld. Since scattered neutrons are
detected mainly in the horizontal plane of the instrument, the magnetic eld thus has to be
applied in the horizontal direction as well. A disadvantage of any horizontal eld magnet
is the limited internal space transparent for neutrons. For this reason, the E4 and FLEX
experiments were accompanied by technical diculties associated with a limited access to
the reciprocal space of the sample.
4.3 Results and discussions
4.3.1 Ordered magnetic structure
DTN crystallizes in the tetragonal I4 space group (#79) with the lattice parameters a =
9.558

A and c = 8.981

A. Nickel ions occupy 2a Wyko positions belonging to the corners
and the center of the chemical body-centered tetragonal unit cell, as shown in Fig. 4.2. The
Laue class and the point group of DTN are 4/m and 4, respectively. The space group I4 is
non-centrosymmetric and has a lattice centering vector C = (0.5, 0.5, 0.5). For the body-
centered space group I4, there is a general reection condition for Bragg peaks Q = (h, k, l),
which is h + k + l = 2n.
We observed magnetic Bragg peaks at Q = (0.5, 0.5, 0.5) (h k l), where h, k and l
are even numbers. The magnetic ordering vector is therefore k = (0.5, 0.5, 0.5). A few
of these peaks are shown in Fig. 4.3. The magnetic ordering vector is invariant under two
symmetry operations: the identity (1) and a two-fold rotation around the tetragonal axis
(2
c
). Therefore, there are two one-dimensional irreducible representations whose characters
are summarized in the character table shown in Tab. 4.1. The decomposition equation for
the magnetic representation is
mag
= 1
1
+ 2
2
.
4.3 Results and discussions 73
1 2
c
1
1 1
2
1 -1
Table 4.1: The character table and the irreducible representations obtained from group
theory analysis for the tetragonal space group I4 (#79) and the magnetic ordering vector
k = (0.5, 0.5, 0.5).
Ni
1
Ni
2
1
(0 0 1) (0 0 -1)
2
(1 0 0) (-1 0 0)

3
(0 1 0) (0 -1 0)
Table 4.2: Three basis vectors calculated for two nickel positions in primitive unit cell.
The three basis vectors presented in Tab. 4.2 are calculated for the two nickel positions
in a unit cell using the projection operator method acting on a trial vector
gG
k
D
(g)
i,g
i
R
g
det(R
g
),
where
is the basis vector projected from the

th
row of the
th
irreducible representation,
D
(g) is the
th
row of the matrix representative of the
th
irreducible representation for
symmetry operation g, i denotes the atomic position and R
g
is the rotational part of the
symmetry operation g. The star of the propagation vector k is formed by two vectors:
k
1
= (0.5, 0.5, 0.5) - symmetry operation (x, y, z)
k
2
= (0.5, 0.5, 0.5) - symmetry operation (-y, x, z)
Magnetic Bragg peaks were measured in a magnetic eld
0
H = 6 T parallel to the
c-axis and at temperatures T < 60 mK. Gaussian function describes very well shapes of
observed reections (see Fig. 4.3) and full widths at half maximum of Gaussians tted to
the data are almost the same as the resolution limit (FWHM 0.57
), indicating that the

system is magnetically long-range ordered. Magnetic scattering was detected neither below
0
H 2 T nor above T 1.4 K. We determined the crystal and magnetic structures of the
deuterated single crystal of DTN using the renement program FullProf. Details of the t of
the nuclear structure are given in the Appendix C. The list of the observed and calculated
2
4SC(NH
2
)
2
Q [F
obs
(Q)[
2
[F
calc
(Q)[
2
(0.5 0.5 0.5) 33.34 (2.68) 9.53
(-0.5 1.5 -0.5) 8.53 (6.79) 5.80
(1.5 0.5 -0.5) 8.43 (1.43) 5.79
(1.5 -0.5 -0.5) 7.98 (1.18) 5.79
(1.5 0.5 0.5) 6.34 (1.11) 7.15
(-0.5 1.5 0.5) 7.89 (4.76) 7.15
(-1.5 1.5 0.5) 2.67 (1.63) 5.92
( 1.5 1.5 0.5) 7.92 (3.22) 5.92
(2.5 0.5 -0.5) 3.70 (1.00) 4.58
(2.5 -0.5 -0.5) 5.69 (1.62) 4.58
(2.5 0.5 0.5) 4.49 (0.89) 5.11
(2.5 1.5 -0.5) 17.49 (5.10) 4.16
(1.5 5.5 -0.5) 1.39 (0.14) 1.57
(-5.5 5.5 0.5) 1.58 (0.70) 0.58
(-2.5 1.5 -0.5) 3.27 (1.00) 4.16
(2.5 -1.5 -0.5) 3.34 (1.02) 4.16
(-2.5 -1.5 -0.5) 4.09 (0.64) 4.16
(1.5 5.5 0.5) 1.12 (0.24) 1.54
Table 4.3: The observed and calculated magnetic structure factors for dierent wave-vectors.
The quality of the t is
2
= 4.89.
magnetic structure factors is given in Tab. 4.3. Using the previously presented result from
the symmetry analysis, we nd that DTN has a collinear arrangement of spins in the ab-
plane at
0
H = 6 T, as shown in Fig. 4.4. The quality of the t of the magnetic structure
is described by
2
= 4.89. The value of the tted ordered magnetic moment in ab-plane
of one nickel ion is equal to m
ab
= 1.941(54)
B
. Based on magnetization measurements
[136], the ferromagnetic component of the ordered moment along the c-axis at
0
H = 6 T is
estimated to be m
c
= 0.8
B
. Hence, the total ordered magnetic moment at
0
H = 6 T is
equal to m
tot
= 2.1
B
, which is close to the saturation value of the fully ordered moment,
m
sat
= 2.34
B
. The quality of the t is independent of the momentum direction in the
ab-plane, indicating an unbroken rotational symmetry.
The experimental data were also tted with a model in which the angle between magnetic
moments located at the corner and the center of the unit cell was xed to 90
. Such a t
has a worse quality (
2
= 5.33) than the t described above and it leads to an unphysical
result which corresponds to a partly disordered magnetic moment at the center of the unit
cell. Therefore we exclude the 90
model from the consideration.

Figure 4.3: Magnetic Bragg peaks observed at the wave-vectors Q = (0.5, 0.5, 0.5), Q =
(0.5, 0.5, 0.5), Q = (1.5, 0.5, 0.5) and Q = (2.5, 1.5, 0.5) are shown in subplots a,
b, c and d, respectively. The measurements were performed in a magnetic eld
0
H = 6 T
applied along the c-axis and at temperatures T < 60 mK.
2
4SC(NH
2
)
2
Figure 4.4: The ordered magnetic structure of DTN. The projections of the magnetic mo-
ments located at the corners and the center of the unit cell on the ab-plane are shown by
black and white arrows, respectively. The rotational symmetry in ab-plane is not broken,
so the magnetic moments can point in any direction in the plane as long as the magnetic
structure remains collinear.
4.3.2 Magnetic phase diagram
To determine the HT phase diagram of DTN, the intensity of the magnetic Bragg reection
at Q = (0.5, 0.5, 0.5) was measured by neutron diraction as a function of magnetic eld
applied parallel to the tetragonal axis. The experiment was performed at constant temper-
atures from T = 0.1 K to T = 0.8 K with the step of T = 0.1 K. Fig. 4.5 shows the eld
scans measured at T = 0.1 K, T = 0.5 K and T = 0.8 K. A fast growth of the antiferro-
magnetic peak intensity above the rst critical eld is observed at all temperatures. After
reaching the top of the dome located near
0
H = 6 T, the magnetic intensities diminish
slowly and nally disappear at the second critical eld, H
c2
. The onset eld of the antiferro-
magnetic phase increases with increasing temperature, consistent with the thermodynamic
measurements. We also observed a decrease of the transition from the antiferromagnetic to
a fully magnetized state with increasing temperature. Fig. 4.7(a) summarizes the antifer-
romagnetic peak intensity measured at the wave-vector Q = (0.5, 0.5, 0.5) as a function
of temperature and eld. The dome-like form of the magnetic phase diagram signies that
thermal uctuations destabilize the ordered magnetic moment, thereby shrinking the area of
the antiferromagnetic phase. The HT phase diagram seen with neutrons conrms the phase
diagram obtained by specic heat and magnetocaloric eect measurements [131].
We investigated whether the magnetic structure always has the same symmetry for all
elds. We measured the eld dependencies of dierent magnetic Bragg peak intensities.
Fig. 4.6 shows the scaled peak intensities detected at the wave-vectors Q = (0.5, 0.5, 0.5),
Q = (2.5, 1.5, 0.5) and Q = (1.5, 1.5, 0.5). The close similarity of the scaled data shows
that the relative intensities of theses peaks is eld independent, providing evidence that the
magnetic structure in the ordered phase has always the same symmetry.
Based on the magnetic phase diagram measured by neutron diraction and the mag-
netic structure, we were able estimate the ordered antiferromagnetic moment as a function
of temperature and eld, because the magnetic Bragg peak intensity is proportional to the
square of the ordered antiferromagnetic moment. The inset in Fig. 4.5 shows that the an-
tiferromagnetic moment increases from zero below H
c1
to m
ab
= 1.941
B
at
0
H 6 T at
T = 0.1 K.
Our experimental investigation is a rst microscopic prove of the ordered transverse spin
components of magnetic moments in the antiferromagnetic phase of DTN, perpendicular to
the eld direction. Together with a preserved rotational symmetry of spin components in the
ab-plane, this result indicates that QPT at H
c1
can be interpret as BEC of magnons.
The magnetic phase diagram as a function of H
a
and H
c
(H
a
and H
c
denotes the component
of the magnetic eld along the crystallographic a- and c-axis, respectively) was determined
by measuring the Bragg peak intensity at the wave-vector Q = (0.5, 0.5, 0.5) as a
function of the angle between the magnetic eld and the tetragonal c-axis. The acceptable
area of the diagram was limited by the dark angles of the horizontal eld magnet. The
color plot of the neutron scattering peak intensity is shown in Fig 4.8 is the H
a
H
c
phase
diagram. The transition from a quantum paramagnetic to antiferromagnetic phase occurs
only if a major component of a magnetic eld is applied along the tetragonal axis. This is a
direct consequence of a strong XY anisotropy: A magnetic eld applied in the xy-plane acts
on a linear combination of the exited states S
z
= 1 mixing it with a ground state S
z
= 0
and thus preventing the system from a magnetic order. Our result independently conrms
the behavior of the rst critical eld as a function of eld angle away from the tetragonal
2
4SC(NH
2
)
2
Figure 4.5: (Color) The neutron scattering intensity measured at the wave-vector Q =
(0.5, 0.5, 0.5) as a function of eld at Q = (0.5, 0.5, 0.5) at temperatures T = 0.1 K, T = 0.5 K
and T = 0.8 K are shown by blue, green and red circles, respectively. The inset shows the
estimated ordered antiferromagnetic moment in ab-plane as a function of eld at T = 0.1 K.
Figure 4.6: The scaled neutron scattering peak intensity measured at Q = (0.5, 0.5, 0.5),
Q = (2.5, 1.5, 0.5) and Q = (1.5, 1.5, 0.5) are shown by black, yellow and green circles,
respectively.
Figure 4.7: (Color) (a) The color plot of the neutron scattering peak intensity measured
at the wave-vector Q = (0.5, 0.5, 0.5) in magnetic elds up to
0
H = 12 T applied along
the tetragonal axis and temperatures up to T = 0.8 K. (b) The antiferromagnetic moment
ordered in the crystallographic ab-plane plotted as function of temperature and magnetic
eld.
axis that was recently determined by the magnetostriction measurements [134].
4.3.3 Bose-Einstein condensation of magnons
The main scientic interest of DTN is a possible eld-induced BEC of magnons. We studied
the energy of the magnetic excitations as a function of magnetic eld using neutron spec-
troscopy. Due to the restrictions from the horizontal-eld magnet, several wave-vectors such
as Q = (0.5, 0.5, 0.5) were not accessible and the constant-Q measurements were performed
at Q = (1.5, 1.5, 1.5).
Fig 4.9 - 4.10 shows the magnetic excitation spectrum at Q = (1.5, 1.5, 1.5) as
a function of energy for dierent magnetic elds strengths. The eld was always applied
along the c-axis. The red lines in the energy scans represent a Gaussian convoluted which
was the instrumental resolution function and tted to the data. The well dened peak at
E = 0.285(5) meV, which is observed at zero eld, splits into two peaks in the presence of
a magnetic eld. This is direct microscopic evidence that the zero-eld magnetic excitations
in DNT are doublet states. The energy of the lower doublet state decreases linearly with
increasing energy, while the energy of the higher doublet state increases with increasing eld.
2
4SC(NH
2
)
2
Figure 4.8: (Color) The color plot of the neutron scattering peak intensity measured at
Q = (0.5, 0.5, 0.5) at magnetic elds up to H = 5.5T applied in crystallographic a- and
c-directions at temperatures below T = 0.1K.
The tted slope of the decrease of the lower doublet and of the increase of the doublet are
0.139(6) meV/T and 0.132(3) meV/T, which is almost the same.
At H
c1
, the energy of the lower doublet is identical to that of the singlet ground state,
leading to a mixing of the lower doublet state with the ground state. As a consequence, the
materials adopts antiferromagnetic long-range order at this eld, as observed in our diraction
experiments. The closing of the energy gap at H
c1
can be described as BEC of magnons,
as it is discussed in Chapter (1). Fig. 4.9(a) shows the summarized eld dependence of the
energy of the doublet. Due to the Zeeman eect, the energy of the higher doublet grows
linearly as a function of magnetic eld in the antiferromagnetic phase. The tted slope of
the increase of energy of the higher doublet is equal to 0.221(4) meV/T. This slope is almost
twice larger compare to one observed in the paramagnetic phase. The increase of the slope
in the ordered phase is a direct consequence of the eld-induced lowering of the energy of the
linear combination of the lower doublet S = 1 and the S
z
= 0 state.
Fig. 4.10 shows the eld dependence of the scattering at Q = (1.5, 1.5, 1.5) in the
ordered phase. A broad peak with a width much larger than the instrumental resolution
is observed between E = 0.35 meV and E = 0.7 meV in the energy scans at
0
H = 4 T
Figure 4.9: (a) The energy of the doublet as the function of magnetic eld applied parallel to
the crystallographic c-axis and measured at wave vector Q = (1.5, 1.5, 1.5). The energy
scans performed in magnetic elds
0
H = 0 T,
0
H = 0.5 T and
0
H = 4 T are shown in
subplots (b), (c) and (d), respectively.
2
4SC(NH
2
)
2
Figure 4.10: Energy scans performed at Q = (1.5, 1.5, 1.5) at
0
H = 4 T,
0
H = 5 T
and
0
H = 6 T are shown in (a), (b) and (c), respectively.
and
0
H = 5 T (see Fig. 4.10(a-b)). Upon increase of magnetic eld to
0
H = 6 T the
broad scattering evolves into a better dened excitation at E 0.4 meV as it is shown
in Fig. 4.10(c). A width larger than the instrumental resolution possibly indicates several
energy levels located close to each other. Our observation of a magnetic mode with the
energy E 0.4 meV at the antiferromagnetic zone center at
0
H 6 T is consistent
with the result of the ESR measurements [137], however its origin is not well understood
yet. Since Dzyaloshinsky-Moriya interactions are forbidden by symmetry of DTN, a possible
explanation of the observed mode could be given based on a distortion of the crystal lattice
in applied magnetic elds.
4.3.4 Spin dynamics in the fully magnetized phase
It is possible that DTN features NNN neighbor interactions between corner and center cell
spins. In this case, the system may be described by the following spin Hamiltonian [139]:
H =
r,
J
(S
z
r
S
z
r+e
+ S
x
r
S
x
r+e
+ S
y
r
S
y
r+e
)
+J
f
r,
S
r
S
r+e
+ D
r
(S
z
r
)
2
g
B
H
r
S
z
r
, (4.1)
where
e
a,

b,
c,
e
c
2

a
2

b
2
,
describes the possibility of a exchange anisotropy and J
f
is the exchange interaction be-
tween two tetragonal spin sublattices. The latter interaction was not considered in previous
descriptions of magnetism in DTN.
The parameters of the spin Hamiltonian 4.1 can be determined best in the fully mag-
netized phase of DTN. This is because the spin-waves can be easily calculated for a ferro-
magnetic phase, giving direct access to the exchange and anisotropy parameters. To test the
Hamiltonian in Eq. (4.1), we performed inelastic neutron scattering measurements above the
second critical eld, at
0
H = 13.3 T.
2
4SC(NH
2
)
2
Spin-wave calculations predict the following one-magnon dispersion in a fully saturated
phase for the Hamiltonian 4.1 [139]:
E
Q
= g
0
H D 2(J
c
+ 2J
ab
) 8J
f
+ 2(J
c
cos(2l)
+J
ab
cos(2k) + J
ab
cos(2h)) + 8J
f
cos(
2h
2
) cos(
2k
2
) cos(
2l
2
). (4.2)
For the Hamiltonian in Eq. (4.1), the second critical eld H
c2
is equal to
g
B
H
c2
= D + 2(1 + )(J
c
+ 2J
a
) + 8J
f
. (4.3)
Based on the equation 4.2, the interaction between two nickel sublattices, J
f
, if present, can
be determined as
J
f
=
1
16
(E
(2 0 0)
E
(1 0 0)
). (4.4)
In a similar way the interaction between spins in ab-plane,
J
ab
=
1
4
(E
(0.5 1 0)
E
(0.5 1.5 0)
). (4.5)
We investigated the dispersion of the low-lying magnetic excitation at
0
H = 13.3 T us-
ing the cold neutron three-axis spectrometer RITA2. Typical energy scans are shown in
Fig. 4.11. The red lines are the result of a Gaussian convoluted with the instrumental reso-
lution function, indicating that the observed magnetic excitations are resolution limited and
long-lived.
The dispersion measured along (h, 0, 0) direction, shown in Fig. 4.12(a), implies the
presence of an exchange interaction between the corner and center spins. These measurements
show that the magnon energy at Q = (2, 0, 0) and Q = (1, 0, 0) dier by 0.111(14) meV.
According to Eq. 4.4, we therefore obtain the value J
f
= 0.07(1) K. In order to obtain
an independent estimate for J
ab
, we performed constant Q-scans at Q = (0.5 1 0) and
Q = (0.5 1.5 0), which are shown in Fig. 4.11 (e) and (f), respectively. The magnon energy
changes by E 0.05 meV between those two reciprocal vectors. According to Eq. (4.5),
Figure 4.11: Energy scans performed in magnetic eld
0
H = 13.3 T at T < 50 mK. Red
lines represent a Gaussian convoluted with the instrumental resolution function.
2
4SC(NH
2
)
2
Figure 4.12: Dispersion of the low-lying magnon measured along dierent reciprocal direc-
tions in magnetic eld
0
H = 13.3 T at T < 50 mK. The blue lines show the spin-wave
dispersion calculated based on the Eq. (4.2) and parameters given in the text.
this corresponds to the exchange interaction in the ab-plane J
ab
= 0.156(4) K, which is in
excellent agreement with an independent determination of J
ab
= 0.16 K [131]. Using these
exchange parameters and Eq. (4.2), we nd good agreement between the dispersion measured
along (0.5, k, 0) direction and calculated as shown in Fig. 4.12(b).
The exchange interaction anisotropy, , and the single-ion XY-anisotropy, D, have the
same wave-vector independent impact on the magnon energy. Therefore those parameters
can not be determined independently from our measurements. We assume that D does not
have a strong eld dependence and keep it xed to the value determined from the zero eld
neutron spectroscopy measurements D = 7.7 K [131]. It allows an estimate of the anisotropy
of the exchange interactions from the magnon dispersion at
0
H = 13.3 T. The best
agreement between the experimental data and the theoretical spin-wave dispersion is found
for = 1.27(1) (see Fig. 4.12). Remarkably, > 1 signies that the exchange interactions
along the crystallographic axes are easy-axis, while the single-ion anisotropy is easy plane.
Due to a magneto-elastic coupling in DTN, it is possible that the single-ion XY-anisotropy
changes in applied elds. In this case our estimate of the exchange interaction anisotropy
will not be precisely correct.
The dispersion calculated using Eq. (4.2) and the parameters D = 7.7 K, J
c
= 2.05 K,
J
a
= 0.156 K, J
f
= 0.07 K and = 1.27 is shown in Fig. 4.12(a-d) for dierent directions
in the reciprocal space, demonstrating excellent agreement with the experimental data. The
second critical eld calculated based on the Eq. (4.3) and the obtained parameters is equal to
0
H
c2
= 12.6 T, which is also in a good agreement with H
c2
measured by specic heat, magne-
tocaloric and magnetization measurements [131, 132]. The proposed spin Hamiltonian (4.1)
with the parameters determined from our neutron spectroscopy experiment provides there-
fore a consistent description of the available macroscopic and spectroscopic data in the fully
magnetized phase of NiCl
2
4SC(NH
2
)
2
.
4.3.5 Spin dynamics at the rst critical eld
We measured the magnetic excitation spectra at the magnetic eld
0
H = 2.1 T applied
parallel to the tetragonal axis and at temperatures T 50 mK. Constant energy scans
along the (1.5, 1.5, l) reciprocal direction, close to the antiferromagnetic zone center, were
2
4SC(NH
2
)
2
carried out at low-energy transfer from E = 0.1 meV to E = 0.4 meV and are shown in
Fig. 4.13. Most scans show two peaks that shift away from each other in wave-vector with
increasing constant energy transfer.
To follow the excitation further, the constant wave-vector scans away from the antiferro-
magnetic zone center were performed (shown in Fig. 4.14). The energy of the lower-energy
mode increases from E 0 meV at the zone center to E = 0.724(19) meV at the antiferro-
magnetic zone boundary. Besides the low-lying mode, we observe a high-energy mode whose
energy increases from E = 0.566(3) meV at the zone center to E = 1.27(3) meV at the zone
boundary. The summarized dispersion is shown in Fig. 4.15. The energy scan carried out
at Q = (1.5, 1.5, 1.5) at
0
H = 2.1 T reveals only one peak corresponding to the higher
doublet excitation. This indicates that the lower excitation is mixed with the ground state
at
0
H = 2.1 T.
Long-dashed blued line in Fig. 4.15 is the result of a linear t of the low-energy data which
demonstrates that
0
H = 2.1 T is possibly larger than the rst critical eld. In this case the
low-lying doublet forms the Goldstone mode, indicating a preserved rotational symmetry.
This may be a direct conrmation that the QPT at H
c1
is BEC of magnons in DTN [138].
However, the liner t describes the low-energy data insuciently. We therefore tted the data
with a quadratic function, as shown by the short-dashed red line in Fig. 4.15. The quadratic
t has a slightly better agreement with the experimental data, indicating that
0
H = 2.1 T
may be somewhat above the critical eld at which BEC of magnons occurs. In this case the
soften low-energy mode mixes with the ground state at the antiferromagnetic zone center
not yet evolving into the Goldstone mode. The short-dashed line shown in Fig. 4.15 is the
t of the high-energy excitation shifted down to zero energy at the antiferromagnetic point.
A comparison of the line slopes close to zero energy shows that the low-energy experimental
data can be described rather by a combination of a linear and a quadratic function then by
only one of them. More precise experimental investigations are needed in this critical region
in order to testify an appearance of the Goldstone mode at H
c1
.
Figure 4.13: Wave-vector scans performed at low-energy transfer in magnetic eld
0
H =
2.1 T applied parallel to the tetragonal axis. Red lines are the result of the instrumental
resolution function convoluted numerically with two Gaussians.
4.3.6 Spin dynamics deep in the antiferromagnetic phase
We also studied the spin dynamics in the antiferromagnetic phase of DTN using neutron
spectroscopy. The measurements focused on energies below 1 meV, and thus track the
development of the lower mode of the doublet into the ordered phase. We did not take
measurements of the higher-lying doublet mode.
Constant wave-vector and energy scans were performed along (1.5, 1.5, l) reciprocal
direction at
0
H = 2.1 T and in two directions - (h, h, 1.25) and (0.6, 0.6, l) at
0
H = 6 T.
The choice of these wave-vectors resulted from the use of the horizontal eld magnet which
restricted greatly the access to the reciprocal plane of the sample. Background scattering
was determined along the (0.6, 0.6, l) direction by measuring the scattering from the sample
rotated away from any magnetic scattering position.
Fig. 4.16 shows the energy scans at
0
H = 6 T performed along (0.6, 0.6, l) from
l = 1.15 to l = 1.5 after the subtraction of the non-magnetic background. Energy scans along
(h, h, 1.25) from h = 0.5 to h = 1 are shown in Fig. 4.20. Two peaks are observed in both
reciprocal directions, indicating a presence of two magnon modes at most wave-vectors. The
2
4SC(NH
2
)
2
Figure 4.14: Energy scans performed in a magnetic eld
0
H = 2.1 T applied parallel to
the tetragonal axis. The result of the numerical convolution of the instrumental resolution
function and Gaussian are shown by red lines.
Figure 4.15: Dispersion of two magnetic excitations measured in a eld
0
H = 2.1 T applied
parallel to crystallographic c-axis at temperatures T < 60 mK. The results of the linear
and quadratic ts of the low-energy data are shown by the long-dashed blue and red lines,
respectively. The dispersion of the higher doublet was tted with a sinusoidal function, as
shown by the long-dashed green line. The short-dashed green line shows the t of higher
doublet shifted down in energy for a comparison.
2
4SC(NH
2
)
2
data was t to a model containing one or two Gaussians convoluted with the instrumental
resolution function. The result is shown by the red lines in Fig. 4.16, indicating that the
observed peaks are resolution limited. The wave-vector dependence of the energies of two
magnetic modes is shown in Fig. 4.18 for both reciprocal directions.
In contrast to the quantum paramagnetic phase of DTN [131], the measurements in the
antiferromagnetic phase at
0
H = 6 T give clear evidence of a splitting of the lower doublet
mode in the ordered phase into two modes, as shown in Fig. 4.18. One magnetic mode has no
dispersion along the (0.6, 0.6, l) direction with an energy E 0.4 meV, as shown by the blue
line in Fig. 4.18(a). The energy of the second mode, shown by green the line in Fig. 4.18(a)
drops from E = 0.589(14) meV at Q = (0.6, 0.6, 1.15) to E = 0.100(7) meV close to the
antiferromagnetic zone center, at Q = (0.6, 0.6, 1.5). The intensity of this mode increases
rapidly as the wave-vector changes from Q = (0.6, 0.6, 1.15) towards Q = (0.6, 0.6, 1.5). In
the (h, h, 1.25) direction we detected two dispersionless modes with energies E
1
0.58 meV
and E
1
0.42 meV (Fig. 4.18(b)).
Our results show that, while there is a considerable dispersion along the c-axis, there is
no measurable change of the excitation energy in the basal plane, as shown in Fig 4.18. The
splitting of the low-energy spin band may arise from the presence of interpenetrating tetrag-
onal spin sublattices. For purely antiferromagnetic order, the two sublattices are completely
decoupled on a mean eld level. In the presence of an external eld, the sublattices are mag-
netized starting to interact with each other. This is because of the non-zero magnetization
of the two sublattice that leads to non-zero magnetic elds from one sublattice on the other.
This coupling may lead to a distortion of the crystal lattice and to additional interactions not
present for H < H
c1
or H > H
c2
. This interpretation is supported by recent magnetostriction
measurements [134] that provide strong evidence for a coupling between the magnetic order
and the lattice.
A high-resolution wave-vector scans performed close to the antiferromagnetic point at
0
H = 6 T revealed the low-energy behavior of the magnetic near the antiferromagnetic
ordering wave-vector, as shown in Fig. 4.19. The observed dispersion was t with a gap and
a quadratic wave-vector dependence. The result plotted as a blue line in Fig. 4.19 indicates
the presence of the energy gap equal to E = 0.135(4) meV. The t gives a gap energy of the
Figure 4.16: Energy scans performed along the (0.6, 0.6, l) reciprocal direction in a magnetic
eld
0
H = 6 T applied parallel to the tetragonal axis after the subtraction of the non-
magnetic background. The measurements were done at T < 60 mK.
2
4SC(NH
2
)
2
Figure 4.17: Energy scans along the (h, h, 1.25) reciprocal direction performed in a magnetic
eld
0
H = 6 T applied along tetragonal axis at T < 60 mK.
Figure 4.18: Low-energy magnetic excitation spectra of DTN, measured along the (0.6, 0.6, l)
and (h, h, 1.25) reciprocal directions in a magnetic eld
0
H = 6 T applied parallel to the
crystallographic c-axis, are shown in (a) and (b), respectively.
dispersive mode comparable to that observed by ESR measurements performed by Zvyagin
and collaborators [137] (see Fig. 4.1), which is equal to E 0.103 meV. Our result thus
independently conrms the gap opening at
0
H = 6 T.
The energy gap observed at
0
H = 6 T can be explained by including second order contri-
butions of J
f
to the spin Hamiltonian 4.1. Quantum uctuations renormalize the parameter
J
f
, as well as J
a
and J
c
in the antiferromagnetic phase of DTN. Therefore the values of
exchange interactions measured in the fully magnetized phase may be somewhat dierent for
the antiferromagnetic state. The spin-wave dispersion measured at
0
H = 6 T (see Fig. 4.18)
is only partly described by the Hamiltonian (Eq. 4.1). In particular, the observed energy
dierence between two at modes along (h, h, 1.25) direction can only be explained by a
rather stronger coupling J
f
than detected by our high-eld measurements. So, the origin
of the two at excitations in this direction cannot be explained by the known Hamiltonian.
This indicates that additional magnetic interactions are present that are presently unknown.
2
4SC(NH
2
)
2
Figure 4.19: Low-energy part of the dispersion of low-lying excitation measured at
0
H = 6 T
applied parallel to the crystallographic c-axis and at T < 60 mK.
4.3.7 Spin dynamics in the antiferromagnetic phase with H ,| c
A dispersion of one-magnon excitation was measured at
0
H = 6 T with the eld turned
away from the crystallographic c-axis by = 20
. Energy scans performed in the wave-vector

range from Q = (0.5, 0.5, 1.5) to Q = (0.5, 0.5, 2) are shown in Fig. 4.20. The red lines
are the results of the instrumental resolution function convoluted numerically with Gaus-
sian, suggesting that all observed peaks are resolution limited. The energy of the observed
excitation is plotted as a function of the wave vector in Fig. 4.21. Comparing Fig. 4.19 and
Fig. 4.21, we see that the energy gap at the zone center remains approximately the same for
0
H = 6 T applied with the angles = 0
and = 20
to the c-axis. Small bumps close

to E = 0.6 meV in the energy performed at Q = (0.5, 0.5, 1.8), Q = (0.5, 0.5, 1.9) and
Q = (0.5, 0.5, 2) (see Fig. 4.20(f-h)) may possibly be related to a mode observed in eld
applied parallel to the tetragonal axis, as shown in Fig. 4.18. Therefore we conclude, that
turning the eld away from the tetragonal axis by = 20
does not qualitatively change the

dispersion of the low-lying magnetic excitation at
0
H = 6 T. This is mainly caused by a
relatively big eld component along the tetragonal axis which is equal to
0
H
c
5.6 T at
= 20
.
Figure 4.20: Energy scans performed along (0.5, 0.5, l) direction in a magnetic eld
0
H =
6 T turned away from the crystallographic c-axis by = 20
and at temperatures T < 60 mK.

2
4SC(NH
2
)
2
Figure 4.21: One-magnon dispersion measured along (0.5, 0.5, l) direction in magnetic eld
0
H = 6 T turned away from the crystallographic c-axis by = 20
and at temperatures
T < 60 mK.
4.4 Summary
We investigated the magnetic phase diagram and the ordered magnetic structure of the
quantum S = 1 quasi-one-dimensional AF NiCl
2
4SC(NH
2
)
2
using neutron diraction. The
ordered magnetic structure in the antiferromagnetic phase of DTN has a collinear antiparallel
spin alignment in crystallographic ab-plane with an unbroken rotational symmetry and the
ordered antiferromagnetic moment equal to m
ab
= 1.922(54)
B
. Thus we prove directly the
order of the spin components, perpendicular to an applied magnetic eld, in DTN, conrming
the interpretation of the QPT at H
c1
as BEC of magnons.
The phase diagram of DTN was studied as a function of magnetic eld and temperature.
Occurring at H
c1
2.1 T, the collinear antiferromagnetic order is canted towards the eld
direction evolving into a fully magnetized phase above H
c2
. A domelike shape of the phase
diagram implies that thermal uctuations prevent the system from magnetic order. Our
study of the magnetic phase diagram as a function of the angle between an applied magnetic
eld and the tetragonal axis, , shows the disappearance of the antiferromagnetic order above
55
.
We measured the one-magnon dispersion in the fully magnetized phase, at
0
H = 13.3 T.
Based on the neutron spectroscopy data, the spin Hamiltonian, exchange interactions and
anisotropy parameters were determined precisely. Importantly, the result indicates a presence
4.4 Summary 99
of a small antiferromagnetic exchange interaction between spin sublattices.
Neutron spectroscopy measurements revealed the splitting of the gapped doublet excita-
tion in applied magnetic eld. At the rst critical eld
0
H 2.1 T the low-lying magnon
mixes with the ground state, which theoretically is described as BEC of magnons.
The study of the dispersion of the low-lying magnon in the antiferromagnetic phase of
DTN reveals the opening of the energy gap at
0
H = 6 T, which we attributed to the presence
of the coupling between tetragonal spin sublattices. However the dispersion of the low-lying
magnon measured in the antiferromagnetic phase is not described completely by the spin
Hamiltonian determined from a high-eld measurements and thus remains unexplained.
2
4SC(NH
2
)
2
Outlook
This work has revealed a number of interesting aspects of low-dimensional quantum magnets,
and raised interesting new questions. The outlook research can be summarized as follows:
(A) Weakly-frustrated S = 1/2 AF on a square lattice, Cu(pz)
2
(ClO
4
)
2
:
1. A fascinating issue is an experimental verication of the predicted collapse of one-
magnon excitations in the 2D S = 1/2 AF on a square lattice close to the saturation
magnetic eld. The main technical diculty is connected with the limitation of avail-
able magnetic elds for neutron scattering experiments to approximately 15 Tesla.
Therefore, the NN spin exchange interaction should be equal to J 0.5 meV at most,
so that the available magnetic elds can reach the saturation-eld limit of the S = 1/2
square-lattice antiferromagnet. Good candidates for future research could be materials
with a signicantly increased distance between copper ions in a square-lattice plane.
2. Another concern in this topic is related to the enhancement of quantum uctuations
by an additional antiferromagnetic NNN exchange interaction. Various numerical cal-
culations predict a rich magnetic phase diagram depending on a strength of NNN
interaction. However, due to a lack of materials, only little is known experimentally
about the predicted and possibly exotic phases of a frustrated S = 1/2 AF on a square
lattice.
(B) Quasi-one-dimensional spin-1 system NiCl
2
4SC(NH
2
)
2
:
3. Our study has shown that the one-magnon dispersion measured in the antiferromagnetic
phase is not well understood. The diculty of the interpretation of the ordered phase
may be due to a relatively strong coupling of the magnetism to the nuclear lattice,
102 Outlook
which leads to magnetic interactions not present at zero or very high elds. The
investigation of the magnetic symmetry breaking in the ordered phase is therefore
an interesting question. Unpublished data from Los Alamos provides evidence of a
eld-induced electric current in the antiferromagnetic phase that could be related to a
change of the electric polarization in this pyroelectric material. This may be similar to
magnetically-induced ferroelectricity in transition metal insulators, with the dierence
that the inversion symmetry is already broken in the paramagnetic phase.
4. The BEC of magnons in DTN can be veried independently by measuring the critical
exponent using neutron scattering. Careful measurements of the magnetic Bragg
peak intensity would be necessary as a function of an applied magnetic eld at dierent
temperatures close to the QCP. Such studies would allow an independent determination
of the critical exponents of the 3D XY antiferromagnetic quantum phase transition.
Appendix A: Symmetry analysis of
Cu(pz)
2
(ClO
4
)
2
The crystal structure of Cu(pz)
2
(ClO
4
)
2
belongs to the monoclinic C2/c space group (#15),
whose Laue class and the point group are 2/m. The Cu
2+
ions occupy 4e Wycko positions
and they are located at r
1
= (0 0.7499 0.25), r
2
= (0 0.2501 0.75), r
3
= (0.5 0.2499 0.25)
and r
4
= (0.5 0.7501 0.75). For C2/c space group, reciprocal lattice points are located at
Q = (h, k, l) with k + l = 2n, l = 2n, k = 2n, h + k = 2n. The magnetic Bragg peak was
observed at Q = (0, 1, 0), so the magnetic ordering vector is given as k = (0, 1, 0). The
ordering wave-vector is dierent from zero due to the C-centering of the lattice.
The subgroup of the ordering wave vector, usually called the little group, consists of four
symmetry operations which belong to four dierent classes: 1, 2
b
,1 and m
ac
. Here, 1 is the
identity, 2
b
is a two-fold rotation around the b-axis, 1 is the inversion and m
ac
is a mirror
plane in the ac plane. Therefore, there are four one-dimensional irreducible representations
whose characters are summarized in the character table given in Tab. 4.4.
1 2
b
1 m
ac
1
1 1 1 1
2
1 1 -1 -1
3
1 -1 1 -1
4
1 -1 -1 1
Table 4.4: The character table and the irreducible representations obtained from group
theory analysis for monoclinic space group C2/c (#15), the table setting choice is b1) and
the magnetic ordering vector k = (0, 1, 0).
The decomposition equation for the magnetic representation is
mag
= 1
1
+1
2
+2
3
+
2
4
. The six basis vectors presented in Tab. 4.5 are calculated for two Cu
2+
positions in
104 Appendix A: Symmetry analysis of Cu(pz)
2
(ClO
4
)
2
X
1
X
2
1
(0 1 0) (0 1 0)
2
(0 1 0) (0 -1 0)
3
(1 0 0) (1 0 0)

4
(0 0 1) (0 0 1)
5
(1 0 0) (-1 0 0)

6
(0 0 1) (0 0 -1)
Table 4.5: Six basis vectors calculated for two Cu
2+
positions in primitive unit cell as ex-
plained in Appendix A.
primitive unit cell using the projection operator method acting on a trial vector
gG
k
D
(g)
i,g
i
R
g
det(R
g
),
where
is the basis vector projected from the

th
row of the
th
irreducible representation,
D
(g) is the
th
row of the matrix representative of the
th
irreducible representation for
symmetry operation g, i denotes the atomic position and R
g
is the rotational part of the
symmetry operation g.
We now analyze the possibility of Dzyaloshinsky-Moriya (DM) exchange interactions in
Cu(pz)
2
(ClO
4
)
2
. DM interactions are described by a Hamiltonian given by
H
DM
=
i,j
D
ij
[S
i
S
j
],
where D
ij
is an axial vector. Action of any symmetry operation (including lattice translations)
A on a DM vector D
ij
must be equal to D
A(i)A(j)
and D
ij
= D
ji
. We analyze the action
of the inversion symmetry operation 1 on the axial DM vector D
12
, where i = 1 and j = 2
denotes the NN copper positions r
1
= (0 0.7499 0.25) and r
2
= (0 0.2501 0.75), respectively.
The result of operation is
1(D
12
) = (D
x
12
D
y
12
D
z
12
).
The application of the inversion symmetry on the ions positions leads to
1(D
12
) = D
1(1)1(2)
= (D
x
21
D
y
21
D
z
21
).
Appendix A: Symmetry analysis of Cu(pz)
2
(ClO
4
)
2
105
These relations imply (D
x
12
D
y
12
D
z
12
) = (D
x
21
D
y
21
D
z
21
) which is possible only in case of
D
12
= 0. Therefore, DM interactions between NN in Cu(pz)
2
(ClO
4
)
2
are forbidden by the
crystal symmetry.
106 Appendix A: Symmetry analysis of Cu(pz)
2
(ClO
4
)
2
Appendix B: The linear spin wave
theory
Assuming that Cu(pz)
2
(ClO
4
)
2
is in the antiferromagnetic N`eel ground state with spins
pointing along z and z direction, we can make the Holstein-Primako transformation of
the spin compounds into bosonic creation and annihilation operators. In linear spin wave
approximation it gives:
S
z
i
= S a
+
i
a
i
, S
z
j
= S + a
+
j
a
j
, S
z
k
= S a
+
k
a
k
,
S
x
i
=
2S
a
i
+ a
+
i
2
, S
y
i
=
2S
a
i
a
+
i
2i
,
S
x
j
=
2S
a
j
+ a
+
j
2
, S
y
j
=
2S
a
j
+ a
+
j
2i
,
S
x
k
=
2S
a
k
+ a
+
k
2
, S
y
k
=
2S
a
k
a
+
k
2i
,
where indexes i, j, and k correspond to a reference spin, its nearest and next nearest neighbor
spins, respectively. The quantization axis lies in bc-plane and therefore J
x
1
= J
z
1
= J, J
y
1
=
J . The spin Hamiltonian written in bosonic operators is:
H =
i,j
4JS(a
+
i
a
i
+ a
+
j
a
j
) + 2S
2J +
2
(a
i
a
j
+ a
+
i
a
+
j
)+
2S
2
(a
i
a
+
j
+ a
+
i
a
j
)+
i,k
4J
2
S(a
i
a
+
k
+ a
+
i
a
k
) (a
+
i
a
i
+ a
+
k
a
k
),
108 Appendix B: The linear spin wave theory
where i, j indicates the sum over NN in the bc-plane and i, k - the sum over NNN in the
bc-plane. After Fourier transformation, the Hamiltonian can be diagonalized using standard
Bogoliubov transformation:
a
q
= u
q
q
+ v
q
+
q
,
a
+
q
= u
q
+
q
+ v
q
q
,
a
q
= v
q
+
q
u
q
q
,
a
+
q
= v
q
q
u
q
+
q
,
where
q
and
q
are the bosonic operators and v
q
, u
q
are numbers. Finally, after the diago-
nalization we have
H
q
= E
g.s.
+
q
S[2A
q
+
q

q
+ B
q
(
+
q

+
q
+
q
q
)], (4.6)
and the eigenstates are given by
h
q
= (A
2
q
B
2
q
)
1/2
, (4.7)
where
A
q
= 4SJ + S(cos(qb) + cos(qc))
4SJ
2
+ 4SJ
2
cos(qb) cos(qc)
and
B
q
= 2S(J 1/2)(cos(qb) + cos(qc)).
The result is shown schematically in Fig. 4.22. Blue and brown colors represent the low and
high energy of the spin wave, respectively. Having a minimum at the antiferromagnetic zone
center Q = (0, 1, 0), the energy of the one-magnon mode increases rapidly in all reciprocal
directions and approaches the maximum at the zone boundary point Q = (0, 1, 0.5). In this
linear approximation, the energy of the spin wave has a local minima at the antiferromag-
netic zone boundary arising from the presence of the NNN exchange interaction. However
the approximation fails to describe the spectra of Cu(pz)
2
(ClO
4
)
2
observed by our neutron
Appendix B: The linear spin wave theory 109
Figure 4.22: The result of the linear spin-wave calculation based on the equation 4.7 is plotted
schematically in coordinates of L and K.
spectroscopy measurements, due to the presence of strong quantum uctuations.
110 Appendix B: The linear spin wave theory
Appendix C: The nuclear structure of
NiCl
2
4SC(NH
2
)
2
Here we show the result of the t of the nuclear structure of NiCl
2
4SC(NH
2
)
2
performed
using the FullProf program. The square of nuclear structure factors for dierent reciprocal
lattice vectors were tted to the observed intensities after a correction of the Lorentz factor.
The goodness of the nal t is equal to
2
= 20.63 and the result is shown in Fig. 4.23. A
scaling factor was obtained from the t of the nuclear structure and was used to estimate
the value of the ordered magnetic moment. The tted positions of atoms in a unit cell of
NiCl
2
4SC(NH
2
)
2
are listed in Tab. 4.6.
112 Appendix C: The nuclear structure of NiCl
2
4SC(NH
2
)
2
Figure 4.23: The result of the calculation of the nuclear structure of DTN. The positions of
open circles correspond to the calculated and observed nuclear structure factors as ordinate
and abscissa, respectively.
Element Position
Ni (0.00000 0.00000 -0.08941)
Cl (1) (0.00000 0.00000 -0.58290)
Cl (2) (0.00000 0.00000 0.09382)
S (0.03271 0.25634 0.03110)
C (0.15359 0.32823 -0.09100)
N (1) (0.19744 0.45836 -0.03954)
N (2) (0.20873 0.25899 -0.19580)
D (1) (0.15452 0.50868 0.01289)
D (2) (0.27245 0.50311 -0.07636)
D (3) (0.27929 0.30479 -0.36183)
D (4) (0.17566 0.16439 -0.26511)
Table 4.6: Fitted positions of atoms in a unit cell of NiCl
2
4SC(NH
2
)
2
Appendix C: The nuclear structure of NiCl
2
4SC(NH
2
)
2
113
[F
measured
(Q)[
2
[F
calculated
(Q)[
2
Q
1 340.0000 415.2000 ( 3 2 -1)
2 236.0000 205.1200 ( 11 0 -1)
3 165.1000 131.3900 ( 4 2 0)
4 1812.6000 2039.9200 ( 9 1 0)
5 281.5000 295.4400 ( 9 0 -1)
6 688.0000 629.3700 ( 2 1 -1)
7 139.4000 37.6700 ( 8 0 0)
8 585.1000 575.2700 ( 10 -2 0)
9 1039.6000 843.0800 ( 4 1 -1)
10 2670.1001 1922.8300 ( 3 1 0)
11 3501.2000 3343.0801 ( 11 -5 0)
12 216.2000 214.9800 ( 10 -3 -1)
13 38.3000 60.7700 ( 9 -2 -1)
14 3431.0000 3886.4099 ( 6 0 0)
15 363.9000 329.5900 ( 10 -5 -1)
16 158.7000 98.9100 ( 10 -6 0)
17 894.5000 864.2600 ( 9 -4 -1)
18 5296.1001 5343.7798 ( 4 0 0)
19 5319.1001 5343.7798 ( 4 0 0)
20 1373.7000 1320.7800 ( 6 -1 -1)
21 99.4000 116.3600 ( 9 -5 0)
22 1240.1000 1291.8800 ( 8 -4 0)
23 2436.5000 1372.2500 ( 2 0 0)
24 367.8000 401.9800 ( 6 -2 0)
25 58.3000 144.8400 ( 711 0)
26 456.0000 499.7400 ( 6 -3 1)
27 1479.7000 1659.5601 ( 7 -5 0)
28 56.7000 31.2400 ( 4 -2 0)
29 2013.1000 2185.8601 ( 6 -6 0)
30 997.0000 913.2800 ( 5 -5 0)
31 1677.3000 1665.1400 ( 5 -6 -1)
32 1738.6000 1522.2800 ( 113 0)
33 1305.4000 1588.8700 ( 4 -6 0)
34 2958.0000 2747.2800 ( 3 -3 0)
35 366.5000 432.5300 ( 3 -4 -1)
36 140.9000 127.1900 ( 1 -11 0)
37 207.9000 206.3800 ( 0 -11 -1)
38 1957.9000 2174.6899 ( 1 -9 0)
39 319.6000 298.1200 ( 0 -9 -1)
40 723.9000 647.8700 ( 1 -2 -1)
41 581.6000 584.5100 ( -2 -10 0)
Table 4.7: The measured and calculated nuclear structure factors for dierent reciprocal
lattice vectors.
2
4SC(NH
2
)
2
[F
measured
(Q)[
2
[F
calculated
(Q)[
2
Q
42 2788.5000 2168.4199 ( 1 -3 0)
43 3540.6001 3589.4099 ( -5 -11 0)
44 213.6000 216.1100 ( -3 -10 -1)
45 889.0000 879.2000 ( -4 -9 -1)
46 1407.0000 1387.3700 ( -1 -6 -1)
47 773.5000 757.8300 ( -8 -9 -1)
48 1294.1000 1323.3700 ( -4 -8 0)
49 415.2000 407.0300 ( -2 -6 0)
50 1497.8000 1687.5100 ( -5 -7 0)
51 1794.5000 1605.5601 ( -9 -7 0)
52 74.2000 73.3600 ( -7 -7 0)
53 483.4000 444.6200 (-12 -5 -1)
54 247.1000 292.1000 ( -5 -6 -1)
55 41.8000 31.2700 ( -2 -4 0)
56 2036.1000 2184.2300 ( -6 -6 0)
57 3419.3999 3398.6599 ( -9 -5 0)
58 1623.5000 1647.9900 ( -6 -5 -1)
59 1204.6000 1265.8300 ( -8 -5 -1)
60 73.5000 76.8800 ( -7 -5 0)
61 1270.6000 1278.7800 (-10 -4 0)
62 815.4000 806.9200 ( -9 -4 -1)
63 1788.6000 1445.8600 (-13 -1 0)
64 1303.4000 1554.4000 ( -64 0)
65 3020.3000 2742.8301 ( -3 -3 0)
66 432.4000 430.1400 ( -4 -3 -1)
67 1454.3000 1351.5601 ( -8 -3 -1)
68 308.4000 85.2400 ( -1 -1 0)
69 202.3000 205.1200 (-11 0 -1)
70 1878.6000 2039.9200 ( -9 -1 0)
71 30.6000 32.2300 ( -6 -2 0)
72 290.0000 295.4400 ( -9 0 1)
73 777.1000 629.3700 ( -2 -1 1)
74 91.9000 99.1800 (-10 1 1)
75 251.4000 219.3400 (-11 4 1)
76 579.2000 575.2700 (-10 2 0)
77 1087.8000 843.0800 ( -4 -1 -1)
78 2657.2000 1922.8300 ( -3 -1 0)
79 3466.1001 3343.0801 (-11 5 0)
80 234.2000 254.1300 (-11 6 -1)
81 212.2000 214.9800 (-10 3 -1)
82 64.2000 41.5100 (-11 7 0)
lattice vectors (continue).
Appendix C: The nuclear structure of NiCl
2
4SC(NH
2
)
2
115
[F
measured
(Q)[
2
[F
calculated
(Q)[
2
Q
83 3476.8999 3886.4099 ( -6 0 0)
84 885.8000 864.2600 ( -9 4 -1)
85 5036.7998 5343.7798 ( -4 0 0)
86 5074.5000 5343.7798 ( -4 0 0)
87 1400.9000 1320.7800 ( -6 1 -1)
88 612.9000 483.2100 ( -9 9 0)
89 755.0000 755.9300 ( -9 8 -1)
90 1197.6000 1291.8800 ( -8 4 0)
91 366.0000 401.9800 ( -6 2 0)
92 1516.5000 1659.5601 ( -7 5 0)
93 1820.8000 1625.8500 ( -7 9 0)
94 55.3000 31.2400 ( -4 2 0)
95 123.8000 123.8800 ( -6 9 -1)
96 2076.2000 2185.8601 ( -6 6 0)
97 3614.7000 3596.3000 ( -5 9 0)
98 1659.5000 1665.1400 ( -5 6 -1)
99 1244.7000 1287.7600 ( -5 8 -1)
100 50.2000 26.0400 ( -2 13 -1)
101 1394.0000 1315.5601 ( -4 10 0)
102 835.0000 820.2400 ( -4 9 -1)
103 1755.7000 1522.2800 ( -1 13 0)
104 1349.4000 1588.8700 ( -4 6 0)
105 2889.3999 2747.2800 ( -3 3 0)
106 374.3000 432.5300 ( -3 4 -1)
107 1174.0000 1396.3900 ( -3 8 -1)
108 308.6000 308.9500 ( -2 9 -1)
109 200.6000 206.3800 ( 0 11 -1)
110 265.5000 117.7700 ( -2 5 -1)
111 2212.0000 2174.6899 ( -1 9 0)
112 26.4000 32.2600 ( -2 6 0)
113 317.3000 298.1200 ( 0 9 -1)
114 785.9000 647.8700 ( -1 2 -1)
115 606.7000 584.5100 ( 2 10 0)
116 1132.6000 876.7200 ( -1 4 -1)
117 2822.7000 2168.4199 ( -1 3 0)
118 3427.3999 3589.4099 ( 5 11 0)
119 222.1000 216.1100 ( 3 10 -1)
120 404.5000 220.9300 ( 3 9 0)
121 702.9000 834.0200 ( 6 9 -1)
122 806.1000 757.8300 ( 8 9 -1)
123 407.4000 407.0300 ( 2 6 0)
124 203.2000 145.6000 ( 7 8 -1)
lattice vectors (continue).
2
4SC(NH
2
)
2
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Acknowledgments
First of all I am grateful to Dr. Michel Kenzelmann for giving me the opportunity to perform
my PhD work in the Laboratory for Neutron Scattering, PSI & ETH Z urich and in the
Laboratory for Solid State Physics, ETH Z urich. For almost four years, he supervised and
encouraged me, giving advice and constructive criticism. I have beneted a lot from working
with Michel. I am thankful to Prof. Dr. Matthias Troyer for accepting to be my supervisor
and also to Prof. Dr. Joel Mesot for agreeing to be my co-examiner and his support.
I greatly appreciated the help provided by the beamline scientists during the neutron scat-
tering experiments: Peter Link and Astrid Schneidewind FRM-2, Arno Heiss, Eric Ressouche
and Beatrice Grenier from ILL, Jorge Gavilano, Niels Christensen and Christof Niedermayer
from SINQ. I also acknowledge the people from the engineering group of LDM at PSI for
helping with sample environment and technical assistance during experiments at SINQ, espe-
cially Markus Zolliker, Christian K agi, Dominik Hohl, Walter Latscha and Stephan Fischer.
I thank Dirk Etzdorf and Harald Schneider for technical assistance at PANDA spectrometer
at FRM2, the technical services of ILL involved during the experiment at IN14 at ILL and
Pascal Fouilloux for technical help during the experiment at D23 at ILL.
I am thankful to the chemists from Clark University, especially to Christopher Landee,
Mark Turnbull and Fan Xiao for providing us with single crystal samples of Cu(pz)
2
(ClO
4
)
2
.
I also think A. Paduan-Filho for the growth of particularly large single-crystals of DTN.
This work wont be complete without theoretical support provided by Rajiv Singh, Tom
Pardini, Cristian D. Batista as well as Vivien Zapf and Marcelo Jaime. I am grateful to them
for a productive collaboration.
Thanks goes to the members of the LNS and LDM, especially to Oksana Zaharko, Kaz-
imierz Conder, Ekaterina Pomjakushina, Volodya Pomjakushin, Denis Cheptiakov and Seva
128 Acknowledgments
Gvasaliya, for useful discussions and support. I am also grateful to Andrey Podlesnyak and
Alex Mirmelstein for all help and assistance in the beginning of my PhD.
Thanks also go to Kruno Prsa, Gelu Marius Rotaru, Roggero Frison, Martin Haag, Johann
Gironnet, Cecile Marcelot, Mohamed Zayed Yasmine Sassa, Gwen Pascua, Martin Mansson,
Yoyo Wang, Marian Stingaciu, Loc LeDreau and Juan Pablo Urrego-Blanco for the great
time we spent together, and that not only in the oce.
I would like to thank my mum Dinara for her unwavering support of my decision to study
physics and my father Lev for his keen endorsement. My warmest thanks are addressed to
Katja Etzel, who not only supported and encouraged me wholeheartedly, but also proofread
some parts of this thesis.
Publications and conferences
2010
The Two-Dimensional Square-Lattice S=1/2 Antiferromagnet Cu(pz)
2
(ClO
4
)
2
N. Tsyrulin, F. Xiao, A. Schneidewind, P. Link, H. M. Rnnow, J. Gavilano
2
, C. P. Landee,
M. M. Turnbull and M. Kenzelmann
Physical Review B 81, 134409 (2010).
2009
Quantum Eects in a Weakly-Frustrated S=1/2 Two-Dimensional Heisen-
berg Antiferromagnet in an Applied Magnetic Field
N. Tsyrulin, T. Pardini, R. R. P. Singh, F. Xiao, P. Link, A. Schneidewind, A. Hiess,
C. P. Landee, M. M. Turnbull, and M. Kenzelmann
Physical Review Letters, 102, 197201 (2009).
Quantum Eects in a Weakly-Frustrated S=1/2 Two-Dimensional Square-
Lattice Antiferromagnet in Zero and Applied Magnetic Field
N. Tsyrulin, T. Pardini, R. R. P. Singh, F. Xiao, P. Link, A. Schneidewind, A. Hiess,
C. P. Landee, M. M. Turnbull, and M. Kenzelmann
ILL Annual report.
Quantum two-dimensional weakly-frustrated S=1/2 antiferromagnet on a
square lattice in zero and applied magnetic elds
Oral presentation at SLS Symposium on Quantum Magnetism, Villigen-PSI, Switzer-
land.
130 Publications and conferences
Magnetic excitation spectra of two-dimensional weakly-frustrated S=1/2
antiferromagnet on a square lattice Cu(pz)
2
(ClO
4
)
2
Oral presentation at 2
nd
FRM2 User Meeting, Garching, Germany.
Quantum two-dimensional weakly frustrated S=1/2 antiferromagnet on a
square lattice in zero and applied elds
Oral presentation at the International Conference on Magnetism, Karlsruhe, Germany.
Quantum eects in a weakly-frustrated S=1/2 two-dimensional antiferro-
magnet in an applied magnetic eld
Poster presentation at MaNEP Swiss Workshop Meeting, Les Diablerets, Switzerland.
2008
Quantum eects in S=1/2 two-dimensional Heisenberg antiferromagnet in
applied magnetic eld
Poster presentation at XXI Congress and General Assembly of the International Union
of Crystallography, Osaka, Japan (Acta Cryst. A64, C416 (2008).
2007
Field dependent ordering temperature in copper pyrazine perchlorate,
Cu(pz)
2
(ClO
4
)
2
C. Landee, F. Xiao, M. Turnbull, N. Tsyrulin, M. Kenzelmann, H. Van Tol
American Physical Society March Meeting.
Curriculum Vitae
Personal data
Name: Nikolay Tsyrulin
Date of birth: 19.11.1983
Place of birth: Kislovodsk/Russian Federation, Russian citizen
Current address
Laboratory for Quantum Magnetism

Ecole Polytechnique Federale de Lausanne
PH D3 324, LQM-IPMC-EPFL, Station 3, 1015 Lausanne, Switzerland
Phone: +41 21 69 34310
E-mail: nikolay.tsyrulin@gmail.com, nikolay.tsyrulin@ep.ch
Education
March 2006 - January 2010: PhD student in the Laboratory for Neutron Scattering ETHZ
& Paul Scherrer Institute and Laboratory for Solid State Physics ETHZ.
Supervisor: Prof. Dr. M. Troyer and Dr. M. Kenzelmann.
September 2000 - January 2006: Moscow State University named after M. V. Lomonosov,
Russian Federation. Diploma in Physics with specialization in Condensed Matter Physics.
Supervisor: Prof. Dr. A. S. Ilyushin.
1990 - 2000: Secondary education, secondary school 15, Kislovodsk, Russian Federation.

Nikolay Tsyrulin - Neutron Scattering Studies of Low-Dimensional Quantum Spin Systems

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diss. eth no.

s uncertainty principle may be present.

Chemical potential Magnetic eld

= S Q(Q S) means that only spin components

( = x, y, z) denotes the spin operator of i

. This transition con-

S(Q, )d dQ. (2.23)

, which was determined by X-ray diraction [117].

A [117]. Tetrahedral perchlorate anions

A), we can not distinguish these two wave-vectors. The magnetic

. The reciprocal (0, k, l) plane of

= 2.34 parallel and perpendicular to the tetragonal

using specic heat and magnetocaloric eect measurements

is the basis vector projected from the

), indicating that the

model from the consideration.

. Energy scans performed in the wave-vector

to the c-axis. Small bumps close

does not qualitatively change the

and at temperatures T < 60 mK.

is the basis vector projected from the

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