Escolar Documentos
Profissional Documentos
Cultura Documentos
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Vibrational spectroscopies
Introduction
Infra-red spectroscopy
Raman spectroscopy
2 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Introduction
3 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Neutron scattering
4 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
5 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Infra-red 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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
7 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Raman effect
8 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
d
4
=
e
e
i
s
d
(40 )2 c 4
9 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
10 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Static approach
Harmonic theory
Eigenfrequencies and eigenmodes calculated using
DFPT/linear response, intensity needed
11 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Selection rules
13 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Vibrational spectroscopies
Introduction
Infra-red spectroscopy
Raman spectroscopy
14 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Infra-red spectroscopy
1
()
15 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
where
MI MJ
2 Etot
uI uJ
with
uI =0,uJ =0
n
eigenmodes eI
2 Etot
uI E
uI =0,E =0
16 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
X
nJ
n
n
eI
eJ
1
Z E0
( i)2 n MI MJ J
17 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
18 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
ZI, = e
| r | v + c.c. + e
ZI
uI
v
I
20 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
hm | [HKS , r] | v i
m 6= n ,
m v
+ [VNL , r]
where [HKS , r] = m~ e r
solve_e.f90
MASTANI Summer School, July 11th 2014
21 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
ZI,
= 2e
X v
v
uI
+ c.c. + e
ZI
zstar_eu.f90
22 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Also
4 X F F
2 2
4 X F F
( )
22
1 =
2 =
where F =
uI
I ZI, M
24 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Vibrational spectroscopies
Introduction
Infra-red spectroscopy
Raman spectroscopy
25 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
26 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
(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
27 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Vibrational spectroscopy & QE
29 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Vibrational spectroscopies
Introduction
Infra-red spectroscopy
Raman spectroscopy
30 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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.:
thresh= 1.306E-08 alpha_mix = 0.700 |ddv_scf|^2 =
13.7
1.010E-14
iter #
8 total cpu time :
291.5 secs
av.it.:
thresh= 1.005E-08 alpha_mix = 0.700 |ddv_scf|^2 =
14.0
4.752E-17
...
32 / 40
Introduction
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
&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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
Usage
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
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
Infra-red spectroscopy
Raman spectroscopy
Using Quantum ESPRESSO
40 / 40