Beruflich Dokumente
Kultur Dokumente
Keith Refson
STFC Rutherford Appleton Laboratory
May 30, 2012
1 / 57
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
IR spectrum
0.8
Absorption
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
0.6
0.4
0.2
1000
2000
3000
-1
Frequency (cm )
4000
2 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
3 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
4 / 57
References
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
5 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
6 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
7 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
More than one atom per unit cell gives rise to optic modes with different
characteristic dispersion.
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
8 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
9 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
X
,
1
E
.u, +
u,
2
.u , + ...
u, .,
,
,, ,
,
(a) =
(a)
is
the
matrix
of
force
constants
,
,
E
At equilibrium the forces u
2E
u, u ,
In the Harmonic Approximation the 3rd and higher order terms are
assumed to be negligible
Assume Born von Karman periodic boundary conditions and substituting
plane-wave u, = m,q exp(iq.R, t) yields eigenvalue equation:
,
D, (q)m,q
2
m,q
= m,q
= p
1
M M
,
C, (q)
= p
1
M M
,
, (a)eiq.Ra
Modelling of
spectra
Intro to Phonons 2012
10 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
0
-2
-1
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
11 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
References
Monatomic
Crystal in 1d (I)
Monatomic
Crystal (II)
Diatomic Crystal
- Optic modes
Characterization
of Vibrations in
Crystals
Formal Theory of
Lattice Dynamics
Quantum Theory
of Lattice Modes
Formal Theory of
Lattice Dynamics
II
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
12 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
13 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
14 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
F,
F,
dF,
d2 E0
=
du
2u
du, du ,
,
Have calculated entire row k , of D,
(q = 0)
Only need 6Nat SPE calculations to compute entire dynamical matrix.
This is a general method, applicable to any system.
Can take advantage of space-group symmetry to avoid computing
symmetry-equivalent perturbations.
Like frozen-phonon method, works only at q = 0.
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
15 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
,
Relies on short-ranged nature of FCM; , (a) 0 as Ra .
Method:
1.
2.
3.
Examples
4.
LO/TO Splitting
,
choose sufficiently large supercell and compute C,
(qsupercell = 0)
using finite-displacement method.
(a).
This object is just the real-space force-constant matrix ,
,
Fourier transform using
,
D,
(q)
Lattice Dynamics
in CASTEP
Modelling of
spectra
or faster.
= p
1
M M
iq.Ra
(a)e
,
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
,
Goal is to calculate the 2nd derivatives of energy to construct FCM or D,
(q).
|i with H
= 2 + VSCF
Energy E = h| H
E
D
d
dE
d h| dV |i
Force F = d = d H |i h| H
d
d
where represents an atomic displacement perturbation.
If h|represents the
Eof H then the first two terms vanish
E ground state
d = n h| d = 0. This is the Hellman-Feynmann
because h| H
d
Theorem.
Force constants are Dthe second
derivatives of energy
E
2
2
d dV
dF
d E
dV d
k = d2 = d = d d |i + h| d d h| ddV2 |i
None of the above terms vanishes.
Second
D derivatives need linear response of wavefunctions wrt perturbation
( d
).
d
In general nth derivatives of wavefunctions needed to compute 2n + 1th
derivatives of energy. This result is the 2n + 1 theorem
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
17 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
can store u(1) (r) in computer repn using basis of primitive cell.
First-order response orbitals are solutions of Sternheimer equation
E
E
(0) (1)
(1) (0)
(0)
H
m m = Pc v m
Lattice Dynamics
in CASTEP
Examples
Greens function (S. Baroni et al (2001), Rev. Mod. Phys 73, 515-561).
Variational DFPT (X. Gonze (1997) PRB 55 10377-10354).
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
The
Frozen-phonon
method
The FiniteDisplacement
method
The Supercell
method
First and second
derivatives
DensityFunctional
Perturbation
Theory
Fourier
Interpolation of
dynamical
Matrices
Lattice Dynamics
in CASTEP
,
Compute D,
(q) on a Monkhorst-Pack grid of q vectors.
Approximation to FCM in p q r supercell given by Fourier transform of
dynamical matrices on p q r grid.
X ,
,
, (a) =
C, (q)eiq.Ra
q
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012
19 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
Examples
LO/TO Splitting
Modelling of
spectra
20 / 57
Methods in CASTEP
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
,
symmetry-independent elements of D,
(q)
q-points in the irreducible Brillouin-Zone for interpolation
electronic k-points adapted to symmetry of perturbation.
Examples
LO/TO Splitting
Modelling of
spectra
21 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
Examples
LO/TO Splitting
Modelling of
spectra
22 / 57
Example output
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
Examples
LO/TO Splitting
Modelling of
spectra
=====================================================================
+
Vibrational Frequencies
+
+
----------------------+
+
+
+
Performing frequency calculation at
10 wavevectors (q-pts) +
+
+
+
Branch number Frequency (cm-1)
+
+ ================================================================= +
+
+
+ ----------------------------------------------------------------- +
+ q-pt=
1 ( 0.000000 0.000000 0.000000)
0.022727
+
+ q->0 along ( 0.050000 0.050000 0.000000)
+
+ ----------------------------------------------------------------- +
+
+
+
1
-4.041829
0.0000000
+
+
2
-4.041829
0.0000000
+
+
3
-3.927913
0.0000000
+
+
4
122.609217
7.6345830
+
+
5
122.609217
7.6345830
+
+
6
165.446374
0.0000000
+
+
7
165.446374
0.0000000
+
+
8
165.446374
0.0000000
+
+
9
214.139992
7.6742825
+
+ ----------------------------------------------------------------- +
23 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
Examples
,
(a). Default is chosen according to MP grid.
,
LO/TO Splitting
Modelling of
spectra
24 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
%BLOCK phonon_supercell_matrix
2 0 0
Set supercell in .cell file, eg 2 2 2 using 0 2 0
0 0 2
%ENDBLOCK phonon_supercell_matrix
,
D, (q)
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
Examples
LO/TO Splitting
Modelling of
spectra
25 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Methods in
CASTEP
A CASTEP
calculation I simple DFPT
Example output
CASTEP phonon
calculations II Interpolation
CASTEP phonon
calculations III Supercell
Running a phonon
calculation
Examples
LO/TO Splitting
Modelling of
spectra
26 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
DFPT with
interpolation -quartz
Supercell method
- Silver
Convergence
issues for lattice
dynamics
Scaling and
other cheats
Examples
LO/TO Splitting
Modelling of
spectra
27 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
1400
1200
Lattice Dynamics
in CASTEP
Examples
DFPT with
interpolation -quartz
Supercell method
- Silver
Convergence
issues for lattice
dynamics
Scaling and
other cheats
1000
-1
ab-initio Lattice
Dynamics
Frequency [cm ]
Lattice Dynamics
of Crystals
800
600
400
200
LO/TO Splitting
Modelling of
spectra
28 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Ag phonon dispersion
3x3x3x4 Supercell, LDA
6
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Examples
DFPT with
interpolation -quartz
Supercell method
- Silver
Convergence
issues for lattice
dynamics
Scaling and
other cheats
(THz)
Lattice Dynamics
in CASTEP
LO/TO Splitting
Modelling of
spectra
29 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
4.
Examples
DFPT with
interpolation -quartz
Supercell method
- Silver
Convergence
issues for lattice
dynamics
Scaling and
other cheats
5.
LO/TO Splitting
Modelling of
spectra
6.
plane-wave cutoff
electronic kpoint sampling of the Brillouin-Zone (for crystals)
(under-convergence gives poor acoustic mode dispersion as q 0
geometry. Co-ordinates must be well converged with forces close to zero
(otherwise calculation will return imaginary frequencies.)
For DFPT calculations need high degree of SCF convergence of
ground-state wavefunctions.
supercell size for molecule in box calculation and slab thickness for
surface/s lab calculation.
Fine FFT grid for finite-displacement calculations.
Accuracies of 25-50 cm1 usually achieved or bettered with DFT.
need GGA functional e.g. PBE, PW91 for hydrogenous and H-bonded
systems.
When comparing with experiment remember that disagreement may be due
to anharmonicity.
Less obviously agreement may also be due to anharmonicity. There is a
lucky cancellation of anharmonic shift by PBE GGA error in OH stretch
modes!
30 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
DFPT with
interpolation -quartz
Supercell method
- Silver
Convergence
issues for lattice
dynamics
Scaling and
other cheats
LO/TO Splitting
Modelling of
spectra
31 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
LO/TO Splitting
32 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
Zincblende BN
Diamond
33 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
diamond
2000
1500
Lattice Dynamics
of Crystals
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
-1
-1
1000
(cm )
Lattice Dynamics
in CASTEP
(cm )
ab-initio Lattice
Dynamics
1500
500
1000
500
0
0
X
X
L WX
L WX
Cubic symmetry of Hamiltonian predicts triply degenerate optic mode at in
both cases.
2+1 optic mode structure of BN violates group theoretical prediction.
Phenomenon known as LO/TO splitting.
34 / 57
LO/TO splitting
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
2
LO
2
T
O
35 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
LO modes can be seen in infrared, INS, IXS experiments, but not raman.
Lattice Dynamics
of Crystals
Exper: G. Raunio et al
250
ab-initio Lattice
Dynamics
200
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
-1
Examples
(cm )
Lattice Dynamics
in CASTEP
150
100
50
()
()
()
(Q)
(Z) X
36 / 57
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
2000
1500
-1
(cm )
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
1000
500
0
Examples
550
540
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
530
520
510
500
490
480
30
60
90
Approach Angle
120
150
180
37 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
q
Z
4
,
q Z ,
,
P
C, (q = 0)(N A) =
0
q q
=V
Z,,alpha
P
F,
=
x,
E
and
Z,
can both be computed via DFPT response to electric field
perturbation.
(Fourier interpolation procedure uses a dipole-dipole model for Coulombic tail
correction of FCM which also depends on Z and . Not included in most
supercell calculations be suspicious of convergence in case of polar systems).
38 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
===============================================================================
Two similar
Optical Permittivity (f->infinity)
DC Permittivity (f=0)
structures
-----------------------------------------------------Zincblende and
diamond
3.52475
0.00000
0.00000
10.00569
0.00000
0.00000
dispersion
0.00000
3.52475
0.00000
0.00000
10.00569
0.00000
LO/TO splitting
0.00000
0.00000
3.52475
0.00000
0.00000
10.00569
DFPT with
===============================================================================
LO/TO splitting
in NaCl
LO/TO splitting
===============================================================================
in non-cubic
Polarisabilities (A**3)
systems
The non-analytic
Optical (f->infinity)
Static (f=0)
term and Born
--------------------------------Charges
5.32709
0.00000
0.00000
19.00151
0.00000
0.00000
Electric Field
0.00000
5.32709
0.00000
0.00000
19.00151
0.00000
response in
CASTEP
0.00000
0.00000
5.32709
0.00000
0.00000
19.00151
Ionic and
===============================================================================
Electronic
Dielectric
Intro to Phonons 2012
39 / 57
Permittivity
Example: NaHF2
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
0.00
2.44
0.00
0.00
0.00
2.49
0 =
5.01
0.00
0.00
0.00
4.71
0.15
0.00
0.15
4.58
(exp: 0 = 4.64/4.43)
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
2.44
0.00
0.00
Z (O1 ) =
2.16
0.08
0.00
0.03
1.04
0.00
0.81
0.14
1.71
Z (Si) =
2.98
0.00
0.00
0.00
3.67
0.30
0.00
0.26
3.45
40 / 57
Example: NaHF2
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
41 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Two similar
structures
Zincblende and
diamond
dispersion
LO/TO splitting
DFPT with
LO/TO splitting
in NaCl
LO/TO splitting
in non-cubic
systems
The non-analytic
term and Born
Charges
Electric Field
response in
CASTEP
Ionic and
Electronic
Dielectric
Intro to Phonons 2012
Permittivity
Example: NaHF2
highly anisotropic Z
xy
0.34
0.69
1.06
z
2.02
1.52
1.04
(H)
(F)
(Na)
42 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
Modelling of spectra
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
43 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
Momentum conservation
ks = ki + kphonon
Typical lattice parameter a0 5 0 kphonon < 0.625 1/
A
For a 5000
A photon, k = 0.00125 1/
A
= optical light interacts with phonons only very close to 0 (the point).
44 / 57
Powder infrared
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
um,,b
Infrared intensity
Im = ,b M Z,a,b
-quartz
0.15
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
Lattice Dynamics
in CASTEP
0.1
0.05
400
600
800
-1
Phonon Frequency (cm )
1000
1200
45 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
46 / 57
Single-crystal infrared
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
q
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
()
q. .q +
q.().q
4 X q.S.q
2 2
0 m m
Non-resonant raman
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
d
d3 E
=
=
d d dQm
dQm
i.e. the activity of a mode is the derivative of the dielectric permittivity with
respect to the displacement along the mode eigenvector.
CASTEP evaluates the raman tensors using hybrid DFPT/finite displacement
approach.
Raman calculation is fairly expensive and is not activated by default (though
group theory prediction of active modes is still performed)
Parameter calculate_raman = true in a task=phonon calculation.
Spectral modelling of IR spectrum is relatively simple function of activity.
(2)4
d
2 h(nm + 1)
=
|e
.I.e
|
S
L
d
c4
4m
with the thermal population factor
nm = exp
~m
kB T
1
48 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
49 / 57
Symmetry Analysis
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
+ -------------------------------------------------------------------------- +
+ q-pt=
1 ( 0.000000 0.000000 0.000000)
0.000765
+
+ q->0 along ( 0.003623 0.000000 0.000000)
+
+ -------------------------------------------------------------------------- +
+ Acoustic sum rule correction <
0.949591 THz applied
+
+
N
Frequency irrep.
ir intensity active
raman active +
+
(THz)
((D/A)**2/amu)
+
+
+
+
1
-0.000975
a
0.0000000 N
N
+
+
2
-0.000719
b
0.0000000 N
N
+
+
3
0.065030
c
0.0000000 N
N
+
+
4
2.533116
d
0.0000000 N
N
+
+
5
3.100104
a
150.2988903 Y
N
+
+
6
3.534759
b
92.9297454 Y
N
+
+
7
3.818109
e
0.0000000 N
Y
+
+
8
10.158077
c
1.7805122 Y
N
+
+
9
11.124650
b
10.9933170 Y
N
+
+
10
11.421874
d
0.0000000 N
N
+
+
11
12.097042
f
0.0000000 N
Y
+
+
12
12.844543
c
2.5718809 Y
N
+
+
13
13.673018
g
0.0000000 N
Y
+
+
14
13.673018
g
0.0000000 N
Y
+
+
15
14.179285
b
22.0325348 Y
N
+
+
16
17.922800
e
0.0000000 N
Y
+
+
17
23.317934
c
121.6365963 Y
N
+
+
18
24.081857
f
0.0000000 N
Y
+
+ .......................................................................... +
50 / 57
Symmetry Analysis
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
..........................................................................
Character table from group theory analysis of eigenvectors
Point Group = 15, D4h
(Due to LO/TO splitting this character table may not contain some symmetry
operations of the full crystallographic point group. Additional
representations may be also be present corresponding to split LO modes.
A conventional analysis can be generated by specifying an additional null
(all zero) field direction or one along any unique crystallographic axis
in %BLOCK PHONON_GAMMA_DIRECTIONS in <seedname>.cell.)
..........................................................................
Rep Mul |
E
2
2
2
I
m
m
m
| -------------------------------a B3u
2 |
1 -1 -1
1 -1
1
1 -1
b B2u
4 |
1 -1
1 -1 -1
1 -1
1
c B1u
4 |
1
1 -1 -1 -1 -1
1
1
d Au
2 |
1
1
1
1 -1 -1 -1 -1
e Ag
2 |
1
1
1
1
1
1
1
1
f B3g
2 |
1 -1 -1
1
1 -1 -1
1
g Eg
1 |
2
0
0 -2
2
0
0 -2
--------------------------------------------------------------------------
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
51 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
52 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
53 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
800
Lattice Dynamics
in CASTEP
Examples
600
-1
(cm )
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
400
200
g(r)
54 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
55 / 57
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
56 / 57
IXS of Diaspore
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
370
365
360
LO/TO Splitting
Modelling of
spectra
Interaction of
light with
phonons
Powder infrared
Accurate
Modelling of
powder IR
Single-crystal
infrared
Non-resonant
raman
Raman scattering
of t-ZrO2
Symmetry
Analysis
Symmetry
Analysis
Inelastic Neutron
Scattering
Intro to Phonons 2012
The TOSCA INS
355
0.00
0.02
0.04
0.06
0.08
0.10
wave vector [A
-1
0.12
0.14
0.16
57 / 57