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Introduction to phonon and spectroscopy calculations in CASTEP

Keith Refson
STFC Rutherford Appleton Laboratory
May 30, 2012

Intro to Phonons 2012

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Motivations for ab-initio lattice dynamics I

Lattice Dynamics
of Crystals

Motivations from experimental spectroscopy:

ab-initio Lattice
Dynamics

Vibrational spectroscopy is sensitive probe of


structure and dynamics of materials.
All experimental methods (IR, raman, INS,
IXS) provide incomplete information.

Lattice Dynamics
in CASTEP
Examples

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Intro to Phonons 2012

IR and raman have inactive modes


Hard to distinguish fundamental and
overtone (multi-phonon) processes in
spectra
No experimental technique provides complete eigenvector information mode
assignment based on similar materials,
chemical intuition, guesswork.

Hard to find accurate model potentials to describe many systems


Fitted force-constant models only feasible for
small, high symmetry systems.

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 II

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

Motivations from predictive modelling

Lattice dynamics calculation can establish stability or otherwise of putative


structure.
LD gives direct information on interatomic forces.
LD can be used to study phase transitions via soft modes.
Quasi-harmonic lattice dynamics can include temperature and calculate
ZPE and Free energy of wide range of systems.
Electron - phonon coupling is origin of (BCS) superconductivity.

Examples
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Modelling of
spectra

Intro to Phonons 2012

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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

Lattice Dynamics of Crystals

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

Books on Lattice Dynamics

M. T. Dove Introduction to Lattice Dynamics, CUP. - elementary


introduction.
J. C. Decius and R. M. Hexter Molecular Vibrations in Crystals - Lattice
dynamics from a spectroscopic perspective.
Horton, G. K. and Maradudin A. A. Dynamical properties of solids (North
Holland, 1974) A comprehensive 7-volume series - more than youll need to
know.
Born, M and Huang, K Dynamical Theory of Crystal Lattices, (OUP, 1954)
- The classic reference, but a little dated in its approach.

References on ab-initio lattice dynamics

K. Refson, P. R. Tulip and S. J Clark, Phys. Rev B. 73, 155114 (2006)


S. Baroni et al (2001), Rev. Mod. Phys 73, 515-561.
Variational DFPT (X. Gonze (1997) PRB 55 10377-10354).
Richard M. Martin Electronic Structure: Basic Theory and Practical
Methods: Basic Theory and Practical Density Functional Approaches Vol 1
Cambridge University Press, ISBN: 0521782856

Lattice Dynamics
in CASTEP
Examples
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Intro to Phonons 2012

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Monatomic Crystal in 1d (I)

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

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Monatomic Crystal (II)

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

Diatomic Crystal - Optic modes

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

Characterization of Vibrations in Crystals

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

Vibrational modes in solids take form of waves with wavevector-dependent


frequencies (just like electronic energy levels).
(q) relations known as dispersion curves
N atoms in prim. cell 3N branches.
3 acoustic branches corresponding to sound propagation as q 0 and
3N 3 optic branches.

ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
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Intro to Phonons 2012

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Formal Theory of Lattice Dynamics

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

Based on expansion of total energy about structural equilibrium co-ordinates


E = E0 +

X
,

1
E
.u, +
u,
2

.u , + ...
u, .,
,

,, ,

where u, is the vector of atomic displacements from equilibrium and

,
(a) =
(a)
is
the
matrix
of
force
constants

,
,

E
At equilibrium the forces u

2E
u, u ,

are all zero so 1st term vanishes.

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

where frequencies are square roos of eigenvalues. The dynamical matrix


,
D, (q)

= p

1
M M

,
C, (q)

= p

1
M M

,
, (a)eiq.Ra

is the Fourier transform of the force constant matrix.

Modelling of
spectra
Intro to Phonons 2012

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Quantum Theory of Lattice Modes

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

The classical energy expression can


be transformed into a quantummechanical Hamiltonian for nuclei.
In harmonic approximation nuclear
wavefunction is separable into product by mode transformation.
Each mode satisfies harmonic oscillator Schroedinger eqn
 with energy
1
levels Em,n = n + 2 ~m for mode
m.
Quantum excitations of modes
known as phonons in crystal
Transitions between levels n1 and
n2 interact with photons of energy
(n2 n1 ) ~m , ie multiples of fundamental frequency m .
In anharmonic case where 3rd -order
term not negligible, overtone frequencies are not multiples of fundamental.

0
-2

-1

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Intro to Phonons 2012

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Formal Theory of Lattice Dynamics II

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

The dynamical matrix is a 3N 3N matrix at each wavevector q.


,
2
D,
(q) is a hermitian matrix eigenvalues m,q are real.
3N eigenvalues modes at each q leading to 3N branches in dispersion
curve.
The mode eigenvector m, gives the atomic displacements, and its
symmetry can be characterised by group theory.

Given a force constant matrix ,


(a) we have a procedure for obtaining
,
mode frequencies and eigenvectors over entire BZ.
In 1970s force constants fitted to experiment using simple models.
1980s - force constants calculated from empirical potential interaction
models (now available in codes such as GULP)
mid-1990s - development of ab-initio electronic structure methods made
possible calculation of force constants with no arbitrary parameters.

ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
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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

ab-initio Lattice Dynamics

Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting
Modelling of
spectra
Intro to Phonons 2012

13 / 57

The Frozen-phonon method

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

The frozen phonon method:

Create a structure perturbed by guessed eigenvector


evaluate ground-state energy as function of amplitude with series of
single-point energy calculations on perturbed configurations.
2
Use E0 () to evaluate k = ddE20
p
Frequency given by k/. ( is reduced mass)
Need to use supercell commensurate with q.
Need to identify eigenvector in advance (perhaps by symmetry).
Not a general method: useful only for small, high symmetry systems or
limited circumstances otherwise.
Need to set this up by hand customised for each case.

Lattice Dynamics
in CASTEP
Examples
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Intro to Phonons 2012

14 / 57

The Finite-Displacement method

The finite displacement method:

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

Displace ion in direction by small distance u.


Use single point energy calculations and evaluate forces on every ion in
+
+
system F,
and F,
for +ve and -ve displacements.
Compute numerical derivative using central-difference formula
+

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
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Modelling of
spectra
Intro to Phonons 2012

15 / 57

The Supercell method

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

The supercell method is an extension of the finite-displacement approach.

,
Relies on short-ranged nature of FCM; , (a) 0 as Ra .

(a) decays as 1/R5


For non-polar insulators and most metals ,
,

For polar insulators Coulomb term decays as 1/R3

Can define cut off radius Rc beyond which ,


(a) is treated as zero.
,
,
,
In supercell with L > 2Rc then C,
(q = 0) = , (a).

Method:

1.
2.
3.

Examples

4.

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Intro to Phonons 2012

,
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
,

to obtain dynamical matrix of primitive cell at any desired q.


,
Diagonalise D,
(q) to obtain eigenvalues and eigenvectors.

This method is often (confusingly) called the direct method.


16 / 57

First and second derivatives

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
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Intro to Phonons 2012

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Density-Functional Perturbation Theory

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

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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

Pc is projection operator onto unoccupied states. First-order potential v (1)


includes response terms of Hartree and XC potentials and therefore depends
on first-order density n(1) (r) which depends on (1) .
Finding (1) is therefore a self-consistent problem just like solving the
Kohn-Sham equations for the ground state.
Two major approaches to finding (1) are suited to plane-wave basis sets:

Lattice Dynamics
in CASTEP
Examples

In DFPT need first-order KS orbitals (1) , the linear response to .


may be a displacement of atoms with wavevector q (or an electric field E.)
If q incommensurate (1) have Bloch-like representation:
(1)
k,q (r) = ei(k+q).r u(1) (r) where u(1) (r) has periodicity of unit cell.

Greens function (S. Baroni et al (2001), Rev. Mod. Phys 73, 515-561).
Variational DFPT (X. Gonze (1997) PRB 55 10377-10354).

CASTEP uses Gonzes variational DFPT method.


DFPT has huge advantage - can calculate response to incommensurate q
from a calculation on primitive cell.
Disadvantage of DFPT - lots of programming required.
18 / 57

Fourier Interpolation of dynamical Matrices

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

DFPT formalism requires self-consistent iterative solution for every separate


q.
Hundreds of qs needed for good dispersion curves, thousands for good
Phonon DOS.

Can take advantage of short-range nature of real-space FCM ,


(a).
,

,
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

Fourier transform using to obtain dynamical matrix of primitive cell at any


desired q, Exactly as with Finite-displacement-supercell method
,
Diagonalise mass-weighted D,
(q) to obtain eigenvalues and eigenvectors.
Longer-ranged coulombic contribution varies as 1/R3 but can be handled
analytically.
Need only DFPT calculations on a few tens of q points on grid to calculate
,
D,
(q) on arbitrarily dense grid (for DOS) or fine (for dispersion) path.

Examples
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Intro to Phonons 2012

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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

Lattice Dynamics in CASTEP

Examples
LO/TO Splitting
Modelling of
spectra

Intro to Phonons 2012

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

CASTEP can perform ab-initio lattice dynamics using

Primitive cell finite-displacement at q = 0


Supercell finite-displacement for any q
DFPT at arbitrary q.
DFPT on M-P grid of q with Fourier interpolation to arbitrary fine set of q.

Full use is made of space-group symmetry to only compute only

,
symmetry-independent elements of D,
(q)
q-points in the irreducible Brillouin-Zone for interpolation
electronic k-points adapted to symmetry of perturbation.

Limitations: DFPT currently implemented only for norm-conserving


pseudopotentials and non-magnetic systems.

Examples
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Intro to Phonons 2012

21 / 57

A CASTEP calculation I - simple DFPT

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

Lattice dynamics assumes atoms at mechanical equilibrium.


Golden rule: The first step of a lattice dynamics calculation is a
high-precision geometry optimisation

Parameter task = phonon selects lattice dynamics calculation.


Iterative solver tolerance is phonon_energy_tol. Value of 1e 5 ev/ang**2
usually sufficient. Sometimes need to increase phonon_max_cycles
Need very accurate ground-state as prerequisite for DFPT calculation
elec_energy_tol needs to be roughly square of phonon_energy_tol
Internal defaults in CASTEP are very adequate, but check that Materials
Studio has not chosen too large a value for elec_energy_tol.
,
D,
(q) calculated at q-points specified on STANDARD (coarse) set
Set may either a symmetry-reduced and weighted M-P grid for DOS or a
k-space path for dispersion.
But it is cheaper and almost always better to use an inperpolation
calculation for DOS and dispersion.

Examples
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Intro to Phonons 2012

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

Intro to Phonons 2012

=====================================================================
+
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
+
+ ----------------------------------------------------------------- +

N.B. 3 Acoustic phonon frequencies should be zero by Acoustic Sum Rule.


Post-hoc correction if phonon_sum_rule = T.

23 / 57

CASTEP phonon calculations II - Interpolation

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

To select set phonon_fine_method = interpolate


,
Specify standard grid of q-points. DFPT D,
(q) will be calculated
explicitly on this grid.
Golden rule of interpolation: Always include the point (0,0,0) in the
interpolation grid. For even p, q, r use shifted grid
phonon_fine_kpoint_mp_offset 0.125 0.125 0.125 to shift one point to
,
D, (q) interpolated to q-points specified on FINE set, which may be grid for
DOS or a dispersion path.
Real-space force-constant matrix is stored in .check file. All fine_kpoint
parameters can be changed on a continuation run. Interpolation is very fast.
can calculate fine dispersion plot and DOS on a grid rapidly from one DFPT
calculation.
Two methods of mapping large supercell dynamical matrix to force constant
matrix.
cumulant method of K. Parlinski (default)
cutoff Parameter phonon_force_constant_cutoff applies real-space cutoff to

,
(a). Default is chosen according to MP grid.
,

LO/TO Splitting
Modelling of
spectra

Intro to Phonons 2012

24 / 57

CASTEP phonon calculations III - Supercell

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

To select set phonon_fine_method = supercell

interpolated to q-points specified in cell file by one of same


phonon_fine_kpoint keywords as for interpolation.
Cumulant or Cutoff method of interpolation applies as for Interpolation
calculation.
Real-space force-constant matrix is stored in .check file.
As with interpolation, all fine_kpoint parameters can be changed on a
continuation run. Interpolation is very fast. can calculate fine dispersion
plot and DOS on a grid rapidly from one DFPT calculation.
Convergence: Need very accurate forces to take their derivative.
Need good representation of any pseudo-core charge density and
augmentation charge for ultrasoft potentials on fine FFT grid. Usually need
larger fine_gmax (or fine_grid_scale) than for geom opt/MD to get good
results.

Examples
LO/TO Splitting
Modelling of
spectra

Intro to Phonons 2012

25 / 57

Running a phonon calculation

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

Phonon calculations can be lengthy. CASTEP saves partial calculation


periodically in .check file if keywords num_backup_iter n or
backup_interval t. Backup is every n q-vectors or every t seconds.
Phonon calculations have high inherent parallelism. Because perturbation
breaks symmetry relatively large electronic k -point sets are used.
Number of k-points varies depending on symmetry of perturbation.
Try to choose number of processors to make best use of k-point parallelism.
If Nk not known in advance choose NP to have as many different prime
factors as possible - not just 2!

Examples
LO/TO Splitting
Modelling of
spectra

Intro to Phonons 2012

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

Intro to Phonons 2012

27 / 57

DFPT with interpolation - -quartz

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

Intro to Phonons 2012

28 / 57

Supercell method - Silver

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

Intro to Phonons 2012

29 / 57

Convergence issues for lattice dynamics

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals
ab-initio Lattice
Dynamics

ab-initio lattice dynamics calculations are very sensitive to convergence issues.


A good calculation must be well converged as a function of
1.
2.
3.

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

Intro to Phonons 2012

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

Scaling and other cheats

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

DFT usually gives frequencies within a few percent of experiment.


Exceptions are usually strongly-correlated systems, e.g. some
transition-metal Oxides where DFT description of bonding is poor.
Discrepancies can also be due to anharmonicity. A frozen-phonon
calculation can test this.
In case of OH-bonds, DFT errors and anharmonic shift cancel each other!
In solid frquencies may be strongly pressure-dependent. DFT error can
resemble effective pressure. In that case, best comparison with expt. may
not be at experimental pressure.
Hartree-Fock approximation systematically overestimates vibrational
frequencies by 5-15%. Commpn practice is to multiply by scaling factor
0.9.
Scaling not recommended for DFT where error is not systematic. Over- and
under-estimation equally common.
For purposes of mode assignment, or modelling experimental spectra to
compare intensity it can sometimes be useful to apply a small empirical shift
on a per-peak basis. This does not generate an ab-initio frequency.

LO/TO Splitting
Modelling of
spectra

Intro to Phonons 2012

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

Two similar structures

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

Zincblende and diamond dispersion

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II

Phonon dispersion curves


BN-zincblende

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

Dipole created by displacement of charges of long-wavelength LO mode


creates induced electric field.
For TO motion E q E.q = 0
For LO mode E.q 6= 0 and E-field adds additional restoring force.
Frequency of LO mode is upshifted.
Lyddane-Sachs-Teller relation for cubic case:

2
LO
2
T
O

LO frequencies at q = 0 depend on dielectric permittivity

35 / 57

DFPT with LO/TO splitting in NaCl

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.

NaCl phonon dispersion


300

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

LO/TO splitting in non-cubic systems

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 frequency varies with angle


in -quartz

Zone Center Frequency (1/cm)

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

In systems with unique axis


(trigonal, hexagonal, tetragonal)
LO-TO splitting depends on direction of q even at q = 0.

530

520

510

500

490

480

30

60

90
Approach Angle

120

150

180

37 / 57

The non-analytic term and Born Charges

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 at q 0 is automatically included in DFPT. At q = 0 exactly,


need to add additional non-analytic term to dynamical matrix
P
P

q
Z

4
,
q Z ,

,
P
C, (q = 0)(N A) =

0
q q

is the dielectric permittivity tensor


is the Born Effective Charge tensor


Z,

=V
Z,,alpha

P
F,
=
x,
E

Z is polarization per unit cell caused by displacement of atom in direction


or force exerted on ion by macroscopic electric field.

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

Electric Field response 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
Examples

Can also apply DFPT to electric field perturbation.


Need trick to evaluate position operator. Evaluate k . See NMR lecture
for details.
set task = efield or task = phonon+efield
Convergence controlled by efield_energy_tol
Computes dielectric permittivity for crystals and polarisability (for
molecules)
Includes lattice contribution for 0 response.
Writes additional file seedname.efield containing () in infrared
region.

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

Ionic and Electronic Dielectric Permittivity

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II

Pure covalent system - Si Z = 0.009,


Ionic system, NaCl. 0 = 6.95, = 2.70. Z (Na) = 1.060,
Z (Cl) = 1.058
-quartz, SiO2 :

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

Note anisotropic tensor character of Z .

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

Unusual bonding, nominally ionic Na+ FHF ,


with linear anion.
Layer structure, R
3 space group.
Phase transition to monoclinic form at 0.4 GPa.

Phonon spectrum measured at ISIS on TOSCA

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

high-resolution neutron powder spectrometer.

No selection rule absences


Little or no anharmonic overtone contamination of spectra
No control over (q, ) path - excellent for
molecular systems but spectra hard to interpret if dispersion present.

41 / 57

Dynamical charges in 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

highly anisotropic Z
xy
0.34
0.69
1.06

z
2.02
1.52
1.04

(H)
(F)
(Na)

charge density n(1) (r) from DFPT


shows electronic response under
perturbation
Charge on F ions moves in response
to H displacement in z direction.

n(1) (r) response to Hx


(blue) and Hz (green)

n(1) (r) response to Ex


(blue) and Ez (green)

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

Interaction of light with phonons

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II

Energy conservation Es = hs = Ei + Ephonon = hi + hphonon

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

In a powder infrared absorption experiment, E field of light couples to electric


dipole created by displacement of ions by modes. Depends on Born effective
charges and atomic displacements.
2
P


1

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

IR Intensity (Arb. Units)

Lattice Dynamics
in CASTEP

0.1

0.05

400

600

800
-1
Phonon Frequency (cm )

1000

1200

Straightforward to compute peak areas.


Peak shape modelling depends on sample and experimental variables.
Multiphonon and overtone terms less straightforward.

45 / 57

Accurate Modelling of powder IR

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II

Need to include optical cavity effects of light interation with crystallite


size/shape. Size/shape shift of LO modes by crystallites.
See E. Balan, A. M. Saitta, F. Mauri, G. Calas. First-principles modeling of the
infrared spectrum of kaolinite. American Mineralogist, 2001, 86, 1321-1330.

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

Prediction of reflectivity of optically flat single crystal surface given as function


of q - projected permittivity q ()

1/2
() 1 2

q
R() = 1/2

() + 1

Lattice Dynamics
of Crystals

ab-initio Lattice
Dynamics
Lattice Dynamics
in CASTEP
Examples
LO/TO Splitting

with q defined in terms of and


mode oscillator strength Sm,

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

() is tabulated in the seed.efield


file written from a CASTEP efield response calculation.
Example BiFO3 (Hermet et al, Phys.
Rev B 75, 220102 (2007)
47 / 57

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

Raman scattering depends on raman activity tensor


raman
I

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

which is implemented in Materials Studio raman calculation.

48 / 57

Raman scattering of t-ZrO2

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

Inelastic Neutron Scattering

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

Thermal neutrons have both energies and momenta of same magnitude as


phonons (unlike photons). Can interact with phonons at any q.
To model spectra need to treat scattering dynamics of incident and emergent
radiation.
In case of INS interaction is between point neutron and nucleus - scalar
quantity b depends only on nucleus specific properties.
kf 2
d2
b S(Q, )
=
dEd
ki
Q is scattering vector and is frequency - interact with phonons at same
wavevector and frequency.
Full measured spectrum includes overtones and combinations and instrumental
geometry and BZ sampling factors.
Need specific spectral modelling software to incorporate effects as
postprocessing step following CASTEP phonon DOS calculation.
A-Climax : A. J. Ramirez-Cuesta Comput. Phys. Comm. 157 226 (2004))

52 / 57

The TOSCA INS Spectrometer

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

ISIS pulsed neutron source at Rutherford Appleton Laboratory, UK


TOSCA - high-resolution powder spectrometer at ISIS
Little or no anharmonic overtone contamination of spectra
No selection rule absences
Signal is weighted DOS integral over BZ

53 / 57

Dispersion, DOS and Gamma

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II
Lattice Dynamics
of Crystals

Phonons represented across the Brillouin Zone by


Dispersion Curve m (k) on high-symmetry
R
P lines
Phonon Density of States g() = dk m (m (k) )

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

INS of Ammonium Fluoride

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

NH4 F is one of a series of ammonium halides


studied in the TOSCA spectrometer. Collab.
Mark Adams (ISIS)
Structurally isomorphic with ice ih
INS spectrum modelled using A-CLIMAX
software (A. J. Ramirez Cuesta, ISIS)
Predicted INS spectrum in mostly excellent
agreement with experiment
NH4 libration modes in error by 5%.
Complete mode assignment achieved.

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

Inelastic X-Ray scattering

Motivations for
ab-initio lattice
dynamics I
Motivations for
ab-initio lattice
dynamics II

IXS spectrometers at ESRF, Spring-8, APS synchrotrons.

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

B. Winkler et el., Phys. Rev. Lett 101 065501 (2008)


380
(0.5, 0, 0) to (0, 0, -0.33)
375
energy [meV]

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

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