VibrationalSpectroscopies IR Raman Lecture Seitsonen

Vibrational Spectroscopy via Computer
Simulations: Raman, Infra-Red and Related

Methods
Ari P Seitsonen
Institut fr Chemie, University of Zurich
NS, Dpartment de Chimie, Paris
MASTANI Summer School, July 11th 2014
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Vibrational spectroscopies
Introduction
Raman spectroscopy
Vibrational spectroscopy & QE
2 / 40
Introduction
Raman spectroscopy
Introduction
Characterisation of the system via its vibrations

Different vibrational spectroscopies
Neutron scattering spectroscopy
Raman spectroscopy
3 / 40
Introduction
Raman spectroscopy
Neutron scattering
Strong scattering at low-Z elements

No charge
Nuclear interaction simple
Magnetic dipole moment, studies of magnetic structures
Low energy, non-distructive
Expensive to produce
Interact weakly with matter, large samples needed
4 / 40
Introduction
Raman spectroscopy
Neutron scattering spectroscopy: Example
5 / 40
Introduction
Raman spectroscopy
Dispersion of light at frequencies comparable with those of
vibrational modes
Wave lengths are macroscopic compared to the size of the
interatomic distance or units cells only q = 0
Linear spectroscopy here; non-linear methods like
multi-dimensional (several photons) like 2D-IR beyond the
scope
6 / 40
Introduction
Raman spectroscopy
Infra-red spectroscopy: Example
7 / 40
Introduction
Raman spectroscopy
Raman effect
8 / 40
Introduction
Raman spectroscopy
Raman scattering spectroscopy

Based on inelastic scattering of light; q 0
Only non-resonant processes possible nowadays
Central quantity: polarisability tensor
Cross section of mode :
2

d
4

=
e
e
i
s
d
(40 )2 c 4
9 / 40
Introduction
Raman spectroscopy
Raman spectroscopy: Example
10 / 40
Introduction
Raman spectroscopy
Static approach
Harmonic theory
Eigenfrequencies and eigenmodes calculated using
DFPT/linear response, intensity needed
11 / 40
Introduction
Raman spectroscopy
Dynamic approach
Molecular dynamics/time evolution of dipole M (IR) or
polarisability (Raman):

Z
M(t)M(t = 0) dt
IIR () FT
t=0

Z
IRaman () FT
(t)(t = 0) dt
t=0
12 / 40
Introduction
Raman spectroscopy
Selection rules
IR: Active modes produce dipole, symmetry operations

transforming like x, y , z
Raman: Active modes produce polarisability, symmetry
operations transforming like xy , yz, zx
13 / 40
Introduction
Raman spectroscopy
Introduction
Raman spectroscopy
14 / 40
Introduction
Raman spectroscopy
Dispersion of light at frequencies comparable with those of

vibrational modes
Coupling of vibrational with electromagnetic modes
Central quantities:
Dielectric function (),
1 = <{()},
2 = ={()}, n
o
Energy-loss =
1
()
15 / 40
Introduction
Raman spectroscopy
IR: System in an electric field

Displacement from equilibrium position uI
Equation of motion:
Xp
I =
MI u
MI MJ DI,J uJ + ZI E ,
J
where
dynamical matrix DI,J = 1
MI MJ
2 Etot
uI uJ
eigenfrequencies n and normalised

Born effective charges ZI =
with
uI =0,uJ =0
n
eigenmodes eI

2 Etot
uI E
uI =0,E =0
16 / 40
Introduction
Raman spectroscopy
IR: Oscillating electric field
Oscillating field E = E0 e(i+)t

0 e(i+)t
Linear order: uI (t) = uI
0
uI
=
X
nJ
n
n
eI
eJ
1
Z E0
( i)2 n MI MJ J
Thus absorption occurs at eigenfrequencies of the system,

with amplitudes Z
17 / 40
Introduction
Raman spectroscopy
IR: Intensity from the dipole
The effective dipole = ZI uI , and the intensity
IIR

2

X X

ZI uI
=

ZI

2 Etot
=
uI E u
I =0,E =0

P
=
uI u
I =0

FI
=
E E =0
(Could be used with finite differences)
18 / 40
Introduction
Raman spectroscopy
IR: Z from DFT

Born-Oppenheimer approximation
(Kohn-Sham) Hamiltonian with a static electric field:
= 0) + V el (E) + V ion (E) ,

H(E)
= H(E
where
V el (E) = eP
E r
ion
V (E) = e I ZI E RI
Isolated system:
R
Pel (E) = e P
n(r) r dr
Pion (E) = e I ZI RI
ZI, = e
X
X
hv | r | v i + e
ZI
uI
v
I
19 / 40
Introduction
Raman spectroscopy
IR: Z from DFT
Using DFPT in linear response regime

X v
X
ZI, = e
| r | v + c.c. + e
ZI
uI
v
I
20 / 40
Introduction
Raman spectroscopy
IR: Position operator in extended system

hm | r | v i not well defined
Recasting
hm | r | v i =
hm | [HKS , r] | v i
m 6= n ,
m v
+ [VNL , r]
where [HKS , r] = m~ e r
Using Greens functions

E

(HKS v ) v = Pm [HKS , r] | v i ,
E

where v = Pm r |v i
solve_e.f90
21 / 40
Introduction
Raman spectroscopy
IR: Born effective charges
ZI,
= 2e
X v
v
uI

+ c.c. + e
ZI
zstar_eu.f90
22 / 40
Introduction
Raman spectroscopy
IR: Dielectric matrix and polarisability
As by-products we obtain
= + 4
P
4 2 Etot
=
,
E
E E
tot
where P = 1 E
E , and
dielec.f90
23 / 40
Introduction
Raman spectroscopy
IR: Dielectric response
Also
4 X F F
2 2
4 X F F
( )
22
1 =

2 =
where F =
uI
I ZI, M
24 / 40
Introduction
Raman spectroscopy
Introduction
Raman spectroscopy
25 / 40
Introduction
Raman spectroscopy
Raman spectroscopy in QE: Implementation
26 / 40
Introduction
Raman spectroscopy
Raman spectroscopy: Intensity

Intensity of eigenmode :
I
(i )4

ei A es (n + 1) ,
where
ei , es = polarisation of incident, scattered photon, n =
Bose-Einstein occupation factor and
X 3 E el
e
I ,
A =
E E uI MI
I
or
A =
X eI
,
uI MI
I
the change in polarisability along a displacement along the

normal mode
27 / 40
Introduction
Raman spectroscopy
Raman spectroscopy: Implementation

An alternative formulation, using the Kohn-Sham density
matrix
X
n(r, r0 ) =
|v i hv | ,
v
E el

V ext
= 2Tr n(r, r )
, (H F theorem)
uI
uI
2

3 E el
n(r, r0 ) V ext
= 2Tr
E E uI
E E uI

n(r,r )
Evaluation of E
E requires six second-order
calculations, independent of number of atoms
28 / 40
Introduction
Raman spectroscopy
Raman spectroscopy: Implementation

Perturbation theory:
2 n(r, r0 )

X (,) E
v
v

=
hv | + P
P
Pv

v
#

X
v 0
v
+
|v 0 i
P|P
hv | + c.c.
0
v

E
E

(,)
v
Terms P
,
P
calculated using Greens

v
functions
Involve V KS /, 2 V KS /(), self-consistency needed
solve_e2.f90
29 / 40
Introduction
Raman spectroscopy
Introduction
Raman spectroscopy
30 / 40
Introduction
Raman spectroscopy
Usage: IR, input
Normal modes
&inputph
tr2_ph
=
prefix
=
amass(1) =
amass(2) =
outdir
=
epsil
=
trans
=
asr
=
fildyn
=
/
0.0 0.0 0.0
for CO2
1e-14
CO2
12.010
15.999
./scratch/
.true.
.true.
.true.
dmat.co2
31 / 40
Introduction
Raman spectroscopy
Usage: IR, output
Electric Fields Calculation

iter #
1 total cpu time :
thresh= 1.000E-02 alpha_mix =
81.9 secs
av.it.:
0.700 |ddv_scf|^2 =
6.7
2.125E-08
iter #
2 total cpu time :
113.7 secs
av.it.:
thresh= 1.458E-05 alpha_mix = 0.700 |ddv_scf|^2 =
14.0
7.433E-08
iter #
7 total cpu time :
261.3 secs
av.it.:
13.7
1.010E-14
iter #
8 total cpu time :
291.5 secs
av.it.:
14.0
4.752E-17
...
End of electric fields calculation
32 / 40
Introduction
Raman spectroscopy
Usage: IR, output

Dielectric constant in cartesian axis
(
(
(
1.097029260
0.034059205
0.000003118
0.034059205
1.097029260
0.000003118
Polarizability (a.u.)^3
20.52
7.44
0.00
7.44
20.52
0.00
0.00
0.00
13.61
0.000000675 )
0.000000675 )
1.063644537 )
Polarizability (A^3)
3.0413
1.1021
1.1021
3.0413
0.0000
0.0000
0.0001
0.0001
2.0166
Effective charges (d Force / dE) in cartesian axis
Ex
Ey
Ez
Ex
Ey
Ez
Ex
Ey
Ez
atom
(
(
(
atom
(
(
(
atom
(
(
(
1
C
1.36251
0.91927
-0.00015
2
O
-0.67618
-0.46117
-0.00032
3
O
-0.67538
-0.46058
0.00009
0.91927
1.36251
-0.00015
0.00000 )
0.00000 )
0.44133 )
-0.46117
-0.67618
-0.00032
-0.00021 )
-0.00021 )
-0.22308 )
-0.46058
-0.67538
0.00009
-0.00009 )
-0.00009 )
-0.22323 )
33 / 40
Introduction
Raman spectroscopy
Usage: Raman, input
&inputph
tr2_ph
prefix
amass(1)
amass(2)
outdir
fildyn
recover
epsil
lraman
trans
fildrho
max_seconds
/
0.0 0.0 0.0
=
=
=
=
=
=
=
=
=
=
=
=
1e-14
gar-w_03-1H
12.0107
1.0079
./scratch/
gar-w_03-1H-ph.dyn
.false.
.true.
.true.
.true.
"gar-w_03-1H-ph.fildrho"
350000
34 / 40
Introduction
Raman spectroscopy
Usage: Raman, output
Raman tensor (au^-1) in cartesian axis

atom
(
(
(
1
0.664735398
-0.007862947
0.000000000
-0.007862947
0.011455170
0.000000000
0.000000000 )
0.000000000 )
0.000420683 )
(
(
(
0.109910490
0.045691031
0.000000000
0.045691031
-0.053438482
0.000000000
0.000000000 )
0.000000000 )
-0.003141788 )
(
(
(
-0.000000000
0.000000000
-0.031312700
0.000000000
-0.000000000
-0.001689833
-0.031312700 )
-0.001689833 )
-0.000000000 )
atom
...
35 / 40
Introduction
Raman spectroscopy
Usage: Raman, output
Raman tensor (A^2)

atom #
1
pol.
0.408888389268E+02
-0.483661299120E+00
0.000000000000E+00
atom #
1
pol.
0.676075372141E+01
0.281052160573E+01
0.000000000000E+00
atom #
1
pol.
-0.277499384006E-19
0.000000000000E+00
-0.192608963659E+01
atom #
2
pol.
-0.408888389268E+02
-0.483661299120E+00
0.000000000000E+00
1
-0.483661299120E+00
0.704624143907E+00
0.000000000000E+00
0.000000000000E+00
0.000000000000E+00
0.258768276476E-01
0.281052160573E+01
-0.328707859334E+01
0.000000000000E+00
0.000000000000E+00
0.000000000000E+00
-0.193255963525E+00
0.000000000000E+00
-0.170828783391E-22
-0.103944090539E+00
-0.192608963659E+01
-0.103944090539E+00
-0.192182381315E-23
-0.483661299120E+00
-0.704624143907E+00
0.000000000000E+00
0.000000000000E+00
0.000000000000E+00
-0.258768276476E-01
...
36 / 40
Introduction
Raman spectroscopy
Usage: Symmetries
Mode symmetry, D_2h (mmm)
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
16)
17)
18)
19)
20)
21)
22)
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
point group:
-43.9
24.8
47.4
73.1
173.8
342.2
350.7
353.0
386.3
530.4
536.8
540.1
560.0
651.0
730.4
732.3
740.5
762.7
826.2
846.5
912.0
912.4
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
B_1u
B_3g
B_3u
B_2u
B_1u
A_u
B_1g
B_3g
B_2g
B_1u
A_g
B_1g
B_2g
B_3u
B_1u
A_u
B_3g
B_3u
B_2u
B_2g
B_2g
A_u
I
R
I
I
I
R
R
R
I
R
R
R
I
I
R
I
I
R
R
...
37 / 40
Introduction
Raman spectroscopy
Usage
Character table for point group D2h

D2h
Ag
B1g
B2g
B3g
Au
B1u
B2u
B3u
E
+1
+1
+1
+1
+1
+1
+1
+1
C2 (z)
+1
+1
1
1
+1
+1
1
1
C2 (y)
+1
1
+1
1
+1
1
+1
1
C2 (x)
+1
1
1
+1
+1
1
1
+1
i
+1
+1
+1
+1
1
1
1
1
(xy)
+1
+1
1
1
1
1
+1
+1
(xz)
+1
1
+1
1
1
+1
1
+1
(yz)
+1
1
1
+1
1
+1
+1
1
linear functions,
rotations
Rz
Ry
Rx
z
y
x
quadratic
functions
x2 , y2 , z2
xy
xz
yz
-
cubic
functions
xyz
3 2
z , y z, xz2
yz2 , x2 y, y3
xz2 , xy2 , x3
38 / 40
Introduction
Raman spectroscopy
Usage: Symmetries
Mode symmetry, D_2h (mmm)
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
freq
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
16)
17)
18)
19)
20)
21)
22)
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
point group:
-43.9
24.8
47.4
73.1
173.8
342.2
350.7
353.0
386.3
530.4
536.8
540.1
560.0
651.0
730.4
732.3
740.5
762.7
826.2
846.5
912.0
912.4
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
[cm-1]
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
-->
B_1u
B_3g
B_3u
B_2u
B_1u
A_u
B_1g
B_3g
B_2g
B_1u
A_g
B_1g
B_2g
B_3u
B_1u
A_u
B_3g
B_3u
B_2u
B_2g
B_2g
A_u
I
R
I
I
I
R
R
R
I
R
R
R
I
I
R
I
I
R
R
...
39 / 40
Introduction
Raman spectroscopy
Usage: Extracting intensities, plotting spectra
Here we use dynmat.x, a simplified version of analysis

Limitations: Beyond LDA only with shortcuts
No ultra-soft PP, PAW with electric field
40 / 40

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VibrationalSpectroscopies IR Raman Lecture Seitsonen

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Available Formats

Vibrational Spectroscopy via Computer

Simulations: Raman, Infra-Red and Related

MASTANI Summer School, July 11th 2014

Using Quantum ESPRESSO

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Characterisation of the system via its vibrations

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Strong scattering at low-Z elements

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Neutron scattering spectroscopy: Example

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Infra-red spectroscopy: Example

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Raman scattering spectroscopy

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Raman spectroscopy: Example

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

IR: Active modes produce dipole, symmetry operations

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Using Quantum ESPRESSO

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

Dispersion of light at frequencies comparable with those of

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

IR: System in an electric field

dynamical matrix DI,J = 1

eigenfrequencies n and normalised

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

IR: Oscillating electric field

Oscillating field E = E0 e(i+)t

Thus absorption occurs at eigenfrequencies of the system,

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

IR: Intensity from the dipole

The effective dipole = ZI uI , and the intensity

(Could be used with finite differences)

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

IR: Z from DFT

= 0) + V el (E) + V ion (E) ,

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014

IR: Z from DFT

Using DFPT in linear response regime

Vibrational spectroscopy & QE

MASTANI Summer School, July 11th 2014