University of Hamburg, Institute of Mineralogy and Petrology

Raman and IR spectroscopy in materials science. Symmetry analysis of normal phonon modes
Boriana Mihailova

Outline

1. The dynamics of atoms in crystals. Phonons 2. Raman and IR spectroscopy :

most commonly used methods to study atomic dynamics

3. Group theory analysis :

phonon modes allowed to be observed in IR and Raman spectra

Atomic dynamics in crystals

Visualization: UNISOFT, Prof. G. Eckold et al., University of Gttingen UNISOFT

KLiSO4, hexagonal

Crystal normal modes (eigenmodes)

Atomic vibrations in crystals = Superposition of normal modes (eigenmodes) e.g.,
a mode involving mainly S-Ot bond stretching

a mode involving SO4 translations and Li motions vs K atoms

Phonons
Atomic vibrations in a periodic solid standing elastic waves normal modes (S, {ui}s ) crystals : N atoms in the primitive unit cell vibrating in the 3D space 3N degrees of freedom finite number of normal states quantization of crystal vibrational energy N atoms 3 dimensions 3N phonons phonon quantum of crystal vibrational energy phonons: quasi-particles (elementary excitations in solids) - En = (n+1/2), - m0 = 0, p = K (quasi-momentum), K q RL - integer spin Bose-Einstein statistics: n(,T)= 1/[exp(/kBT)-1] (equilibrium population of phonons at temperature T)
Harmonic oscillator n=3 n=2 n=1 n=0 2

Phonon frequencies and atom vector displacements a

m1 K m2 Atomic bonds elastic springs Hookes low : mx = Kx

K m

Equation of motion for a 3D crystal with N atoms in the primitive unit cell :

wi ,q = Dii ', ' (q) wi ' ',q

2 i ' '

wi ,q =

1 mi

u i , q

= 1,2,3

i = 1,..., N

atomic vector displacements dynamical matrix

Dss ' ' (q) =

1 m s ms '

ss ' ' (q)

second derivatives of the crystal potential

in a matrix form:

2 w q = D(q) w q
(3N1) (3N3N) (3N1)

(D(q) ) w
2

=0

phonon S, {ui}s eigenvalues and eigenvectors of D = f (mi, K({ri}), {ri}) phonon S, {ui}s carry essential structural information !

Types of phonons
diatomic chain Acoustic phonon: u1, u2, in-phase Optical phonon: u1, u2, out-of-phase phonon dispersion: ac(q) op(q), for q 0, op > ac
qa qa chain in 1D chain in 3D

3D crystal with N atoms per cell : 3 acoustic and 3N 3 optical phonons induced dipole moment
interact with light

1 Longitudinal: wave polarization (u) || wave propagation (q) Longitudinal 2 Transverse: wave polarization (u) wave propagation (q) Transverse

LA

LO

TA

TO

Phonon (Raman and IR) spectroscopy

electromagnetic wave as a probe radiation (photon opt. phonon interaction): Infrared absorption:
( phonon ( phonon photon = EES ) EGS )

, k

excited state ground state

Raman scattering inelastic light scattering from optical phonons

anti-Stokes Stokes

, ki
s = i
Stokes

, ks
s

ks = ki K

s = i +

anti-Stokes

ks = ki + K

Phonon (Raman and IR) spectroscopy

only optical phonons near the FBZ centre are involved
K max = k 2ki (e.g. Raman, 180-scattering geometry) ki k s = K K max << i (IR, vis, UV) ~ 103 105 ki ~ 10-5 10-3 Kmax (a ~ 10 ) a photon-phonon interaction only for K 0 E= ck = c(2/) = hc(1/) spectroscopic units: cm-1
10 [cm-1] 1.24 [meV] 10 [cm-1] 0.30 [THz] [].[cm-1] = 108

IR and Raman spectra are different for the same crystal

different interaction phenomena

different selection rules !

Raman and IR intensities

IR activity: induced dipole moment due to the change in the atomic positions activity

= ( x , y , z )
(Q) = 0 + Qk + ... Qk
Qk configurational coordinate

0, IR activity IR: asymmetrical, one-directional Raman activity: induced dipole moment due to deformation of the e- shell activity

xx Polarizability tensor: = xy xz

(Q) = 0 +

Qk + ... Qk

xy xz yy yz yz zz

P = .E
induced polarization (dipole moment per unit cell)

0, Raman activity Raman: symmetrical, two-directional

N.B.! simultaneous IR and Raman activity only in non-centrosymmetric structures

Raman and IR activity in crystals

Isolated TO4 group
a c

Crystal: Pb3(PO4)2, R3m

b

Pb2 Op P

a c

Pb2 Op P

Pb1

Ot

Pb1

Ot

Raman-active

Raman-active
a c b

IR-active
a b c

Pb2 Op P

Pb2 Op P

Pb1

Ot

Pb1

Ot

IR-active Raman-active IR-active

Methods for normal phonon mode determination

Three techniques of selection rule determination at the Brillouin zone centre: Factor group analysis
the effect of each symmetry operation in the factor group on each type of atom in the unit cell

Molecular site group analysis

symmetry analysis of the ionic group (molecule) site symmetry of the central atom + factor group symmetry

Nuclear site group analysis

site symmetry analysis is carried out on every atom in the unit cell set of tables ensuring a great ease in selection rule determination preliminary info required: space group and occupied Wyckoff positions
Rousseau, Bauman & Porto, J. Raman Spectrosc. 10, (1981) 253-290

Bilbao Server, SAM, http://www.cryst.ehu.es/rep/sam.html N.B.! Tabulated information for: first-order, linear-response, non-resonance interaction processes
(one phonon only) (one photon only) (i < EESelectron-EGSelectron)

Symbols and notations

Symmetry element Identity Rotation axes Mirror planes to n-fold axis || to n-fold axis bisecting (2,2) Inversion Rotoinversion axes Translation Screw axes Glide planes Schnflies notation E Cn International (Hermann-Mauguin) 1 n = 1, 2, 3, 4, 6 m m, mz mv, md, m

h v d

I Sn tn k Cn

1 n = 1 , 2 , 3, 4, 6 tn nk
a, b, c, n, d

Point groups:
Triclinic C1 Ci 1 1 Monoclinic C2 CS C2h C2v D2 D2h 2 m 2/m mm2 222 mmm Trigonal (Rhombohedral) C3 C3i C3v D3d D3 3 3 3m 3m 32 Tetragonal C4 S4 C4h C4v D2d D4 D4h 4 4 4/m 4mm 42m 422 4/mmm Hexagonal C6 C3h C6h C6v D3h D6 D6h 6 6 6/m 6mm 6m2 622 6/mmm Cubic T Th Td O Oh 23

m3
4 3m 432 m3 m

Dn: E, Cn; nC2 to Cn; T: tetrahedral symmetry;

O: octahedral (cubic) symmetry

Symbols and notations

normal phonon modes Reminder:

irreducible representations
C3 (3)
r3

Symmetry element: matrix representation A Character: Tr ( A ) =

A
i

ii

v (m)
r1

Point group

Symmetry elements

characters

C3v (3m)
reducible

1 3

3 0 1 -1 0

r2

m 1 1 0 1 m: 3: 1:

1 0 0 0 1 0 0 0 1
0 1 0 0 0 1 1 0 0

1 0 0 0 1 0 0 0 1
0 1 0 1 2 3 0 2 0 3 2 1 2

irreducible

A1 E A1 + E

1 2 3

Mulliken symbols

1 0 0 0 0 1 0 1 0

1 0 0 0 1 0 0 0 1

reducible

irreducible (block-diagonal)

Mulliken symbols
A, B : 1D representations non-degenerate (single) mode
only one set of atom vector displacements (u1, u2,,uN) for a given wavenumber

A: symmetric with respect to the principle rotation axis n (Cn) B: anti-symmetric with respect to the principle rotation axis n (Cn) E: 2D representation doubly degenerate mode
two sets of atom vector displacements (u1, u2,,uN) for a given wavenumber

T (F): 3D representation triply degenerate mode

three sets of atom vector displacements (u1, u2,,uN) for a given wavenumber

subscripts g, u (Xg, Xu) : symmetric or anti-symmetric to inversion 1 superscripts , (X, X) : symmetric or anti-symmetric to a mirror plane m subscripts 1,2 (X1, X2) : symmetric or anti-symmetric to add. m or Cn

2D system
Y X E mode

3D system
Y Z X

T mode

Bilbao Crystallographic Server, SAM

Working example: CaCO3, calcite, R3c (167) D3d6
(0,0,0)+ (2/3,1/3,1/3)+ (1/3,2/3,2/3)+

Ca: (6b) 0 0 C : (6a) 0 0 O : (18e) 0.25682 0

0 0.25 0.25

http://www.cryst.ehu.es/

or google Bilbao server

or input, then click

Bilbao Crystallographic Server, SAM

Calcite

Ca: (6b) 0 0 C : (6a) 0 0 O : (18e) 0.25682 0

0 0.25 0.25

Bilbao Crystallographic Server, SAM

Calcite
Point group
number of operation of each class symmetry operations

selection rules
Raman-active xx = yy zz
non-zero components

IR-active z 0 x , y 0 xx = -yy xy xzyz

(xz,yz)

+ acoustic

rotation (inactive)

normal modes
Ca: (6b) : C : (6a) : O : (18a) :

characters

A1u + A2u + 2Eu acoustic: A2u+Eu (the heaviest atom) A2g + A2u + Eg + Eu A1g + A1u + 2A2g + 2A2u + 3Eg + 3Eu

(N = 6:3 +6:3+18:3 = 10) Total: 10A + 10E = 30 3N = 30 opt = A1g(R) + 2A1u(ina) + 3A2g(ina) + 3A2u(IR)+ 4Eg(R) + 5Eu(IR)

5 Raman peaks and 8 IR peaks are expected

Spectra from

4 3 1

Spectra of Calcite from Hamburg,

Raman-active = A1g + 4Eg IR-active = 3A2u + 5Eu

Bilbao server, SAM

Practical exercise: number of expected Raman and IR peaks of aragonite exercise

CaCO3, aragonite, Pnma (62) D2h16 Ca C O1 O2 : : : : (4c) (4c) (4c) (8d) 0.24046 0.25 0.4150 0.08518 0.25 0.76211 0.09557 0.25 0.92224 0.08726 0.47347 0.68065

Solution: Solution opt = 9Ag(R) + 6Au(ina) + 6B1g (R) + 8B1u (IR) + 9B2g (R) + 5B2u (IR) + 6B3g (R) + 8B3u (IR) 30 Raman peaks and 21 IR peaks are expected

Spectra of CaCO3

Calcite: Raman-active = A1g + 4Eg Aragonite:

Raman-active = 9Ag + 6B1g + 9B2g + 6B3g

22 observed

Bilbao server, SAM

Perovskite-type structure ABO3
double perovskite-type single perovskite-type

chemical B-site disorder chemical 1:1 B-site order

A(B,B)O3 Pm3 m (221) O 1 h A: (1b): 0.5 0.5 B/B: (1a): 0 0 O: (3d): 0.5 0 0.5 0 0

AB0.5B0.5O3 Fm3 m (225) O 5 h

(0,0,0)+ (0,1/2,1/2)+ (1/2,0,1/2)+ (1/2,1/2,0)+

A : B : B: O :

(8c) : (4a) : (4b) : (24e):

0.25 0 0.5 0.255

0.25 0 0 0

0.25 0 0 0

Bilbao server, SAM

A(B,B)O3 Pm3 m (221) O 1 h A: (1b): T1u B: (1a): T1u O: (3d): 2T1u + T2u
Total: 5T = 15
acoustic

3N (5 atoms)

opt = 3T1u(IR) + T2u(ina)

y x

BO6 stretching (3 sets) BO6 bending (3 sets) (3 sets) B-c. transl.

Bilbao server, SAM

AB0.5B0.5O3 Fm3 m (225) O 5 h Exercise: determine the atom vector displacements for A1g, Eg, T2g, and add. T1u Exercise A: B: B: O: (8c): (4a): (4b): (24e):
T1u acoustic T1u + T2g T1u T1u A1g + Eg + T1g + 2T1u + T2g + T2u

Total: 1A+1E+ 9T = 30

3N (N=8:4+4:4+4:4+24:4)

opt = A1g + Eg + T1g(ina) + 3T1u(IR) + T2u(ina)

A1g Eg T2g T2g T1u

z y x

Bilbao server, SAM

Perovskite-type structure ABO3 : ferroelectric phases

BaTiO3

1 Pm3 m (221) O h

cubic

Ba: (1a): 0.0 0.0 0.0 Ti: (1b): 0.5 0.5 0.595 O: (3c): 0.5 0 0.5

tetragonal
14 Amm2 (38) C 2v

orthorhombic
5 R3m (160) C 3v

rhombohedral

P4mm (99) C
Ba: (1a): Ti: (1b): O1: (1b): O2: (2c): 0.0 0.5 0.5 0.5

1 4v

(0,0,0)+ (0,1/2,1/2)+ 0.0 0.595 -0.025 0.489 Ba: (2a): Ti: (2b): O1: (2b): O2: (4c): 0.0 0.5 0.5 0.5 0.0 0.5 0.5 0.264 0.0 0.515 0.009 0.248 Ba: (1a): 0.0 0.0 0.0 Ti: (1a): 0.4853 0.4853 0.4853 O: (1b): 0.5088 0.5088 0.0185

0.0 0.5 0.5 0.0

Bilbao server, SAM

Perovskite-type structure ABO3 : ferroelectric phases

BaTiO3
Ba: Ti: O:

Pm3 m
T1u T1u T1u T1u T2u Ba: Ti: O1: O2:

P4mm
A1 + E A1 + E A1 + E A1 + E B1 + E Ba: Ti: O1: O2:

Amm2
A1 + B1 + B2 A1 + B1 + B2 A1 + B1 + B2 A1 + B1 + B2 A1 + A2 + B2

R3m
Ba: A1 + E Ti: A1 + E O: A1 + E A1 + E A2 + E

Polar modes: modes simultaneously Raman and IR active

mode polarization along (~ u)

LO: q || TO: q

xxz, yyz, zzz

Experimental geometry
Infrared transmission (only TO are detectible)

IIR 2

Iinc
Y Z X

Itrans
polarizer

Imeas
z

or
y

Raman scattering

Portos notation: A(BC)D

A, D - directions of the propagation of incident (ki) and scattered (ks) light, B, C directions of the polarization incident (Ei) and scattered (Es) light

IRaman
Y

back-scattering geometry Z

ks
X

(qx,0,0)

X (YY ) X

X ( ZZ ) X

X (YZ ) X

Ei Es

Ei Es

Ei

Es

ki ks
Y ( XY ) X

(ki = ks+q , E is always to k)

yy yyn

zz zzn

yz yzn
Y ( ZZ ) X

n=x n = y, z

LO TO

right-angle geometry

Y Z X

Y ( XZ ) X Y ( ZY ) X

ki

(qx,qy,0)

xy xyn

xz xzn

zy zyn

zz zzn

n = x,y n=z

LO+TO TO

Experimental geometry cubic system

e.g., Td ( 4 3m )

X Y Z

ks ki ki = ks + q
q = (0,0, q z )

Ei Es Ei Es

Z (YY ) Z

yy
z xy

A1, E

Z (YX ) Z
x yz

q ||

T2(LO)

= (0,0, z )
q x || = ( x ,0,0) q z
y xz

X Y Z

ks Ei Es ki
q = (q x ,0, q z )

X ( ZY ) Z
X ( ZX ) Z

T2(LO+TO)

Ei Es

T2(TO)

= (0, y ,0)

Experimental geometry non-cubic system

e.g., trigonal, C3v (3m)
(hexagonal setting)

X Y Z

ks ki Ei Es

z Z (YY ) Z yy
x yy

= (0,0, z ) q = (0,0, q z )
= ( x ,0,0)

A1(LO) E(TO) E(TO)

Ei Es
Z Y X Y Y Z X

Z (YX ) Z

y xy

= (0, y ,0) q = (0,0, q z )

ks ki ks ki Ei Es Ei Es

z Y ( ZZ )Y zz

q = (0, q y ,0)

= (0,0, z )

A1(TO)

X (Y 'Y ' ) X
contribution from

x yy
z yy

= ( x ,0,0)

q = (q x ,0,0)

E(LO) A1(TO)

= (0,0, z )

LO-TO splitting
More peaks than predicted by GTA may be observed (info is tabulated)
Cubic systems: LO-TO splitting of T modes: T(LO) + T(TO) systems Non-cubic systems: {A(LO) ,A(TO)}; {B(LO),B(TO)}; {E(LO),E(TO)} systems
general rule:

( LO) > (TO)

(the potential for LO: U+E; for TO: U)

Cubic crystals: LO-TO splitting covalency of atomic bonding crystals LO-TO: larger in ionic crystals, smaller in covalent crystals Uniaxial crystals: if short-range forces dominate: if long-range forces dominate :

A
TO LO

E
TO LO

TO
A E

LO
A E

Raman shift (cm-1)

Raman shift (cm-1)

under certain propagation and polarization conditions quasi-LO and quasi-TO phonons of mixed A-E character

LO-TO splitting
LO-TO splitting: sensitive to local polarization fields induced by point defects

I23 (T03)
Bi(24f), Si(2a), O1(27f), O2(8c), O3(8c)

Bi12SiO20:X

Bi4Ge3O12:Mn
0.8991018 cm-3

I 4 32 (Td6)
Bi(16c), Ge(12a), O(48e)

0.476 0.094 undoped

Raman shift / cm-1

Raman shift / cm-1

a change in ILO/ITO depending on type and concentration of dopant

One-mode / two-mode behaviour in solid solutions

different types of atoms in the same crystallogr. position, e.g. (B1-xBx)Oy

two-mode behaviour:

two peaks corresponding to pure B-O and B-O phonon modes

intensity ratio I(B-O )/I(B-O ) depends on x covalent character of chemical bonding : short correlation length relatively large difference in f(B/B-O) and/or m(B/B)

one-mode behaviour:
one peak corresponding to the mixed B-O/B-O phonon mode ~ lineal dependence of the peak position on dopant concentration x ionic character of chemical bonding : long correlation length similarity in ri(B/B), f(B/B-O) and m(B/B)

intermediate classes of materials: two-mode over x (0, xm) and one-mode over x (xm, 1)

One-mode / two-mode behaviour in solid solutions

one-mode behaviour PbSc0.5(Ta1-xNbx)0.5O3 two-mode behaviour Pb3[(P1-xAsx)O4]2
T > TC

f m

Non-centrosymmetric crystals with compositional disorder

LO-TO splitting + one-mode/two-mode behaviour: we may observe four peaks instead of one !

Transformation of polarizability tensors

Y Z X

a 0 0 0 a 0 0 0 a 0 b 0 0 0 b 0 0 2b
3b 0 0 0 3b 0 0 0 0

rotZ(=45) = UT U

a 0 0 0 a 0 0 0 a
0 b 0 0 0 b 0 0 2b
0 0 d 2 0 0 d 2 d 2 d 2 0 0 0 d 2 0 0 d 2

Y Z X

0 3b 0 3b 0 0 0 0 0
d 2 d 2 0

0 d 0 0 0 0 0 0 d d 0 0 0 0 d 0 0 0 0 0 0 0 d 0 d 0 0
0.20
1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

d 0 0 d 0 0

0 0 0

PSTcpp 0 deg, p-pol. PSTdpp 45 deg, p-pol.

0.15

PSTccp 0 deg, c-pol. PSTdcp 45 deg, c-pol.

Intensity / a.u.

Intensity / a.u.

A1g(O) + Eg(O)

F2g(O) + F2g(Pb)
0.10

I(F2g )

I(Eg )

0.05

0.00

100

200

300

400

500

600
-1

700

800

900

100

200

300

400

500

600
-1

700

800

900

Raman shift / cm

Raman shift / cm

Conclusions

Group theory: predicts the number of expected IR and Raman peaks

one needs to know: crystal space symmetry + occupied Wyckoff positions Deviations from the predictions of the group-theory analysis: LO-TO splitting if no centre of inversion (info included in the tables) one-mode two-mode behaviour in solid solutions local structural distortions (length scale ~ 2-3 nm, time scale ~ 10-12 s) Experimental difficulties (low-intensity peaks, hardly resolved peaks)

What should we do before performing a Raman or IR experiment?