Insulators, polarization, and electric fields from first principles

Polarization, electric fields, and
dielectric response in insulators
David Vanderbilt
Rutgers University
Conference on Computational Physics, Los Angeles, 2005

http://www.physics.rutgers.edu/~dhv/talks/ccp05.pdf
Outline
Introduction
Electric polarization
What is the problem?
What is the solution?
Electric fields
Localized description:
Wannier functions
Dielectric and piezoelectric properties
Systematic treatment of E-fields and strains
Mapping energy vs. polarization
Summary and prospects

Collaborators
Principal Contributors:
D. King-Smith Polarization
N. Marzari Wannier functions
R. Nunes
I. Souza Electric fields
J. Iniguez
N. Sai
O. Dieguez Mapping E vs. P
K. Rabe
X. Wu Systematic DFPT in E and strain
D. Hamann
X. Wang DFPT in presence of E-field

Principal References
Polarization
R.D. King-Smith and D. Vanderbilt, Phys. Rev. B 47, 1651 (1993).
Review on polarization
R. Resta, Rev. Mod. Phys. 66, 899 (1994).
Dynamics of polarization
I. Souza, J. Iniguez and D. Vanderbilt, Phys. Rev. B 69, 085106 (2004).
Finite electric field
R.W. Nunes and X. Gonze, Phys. Rev. B 63, 155107 (2001).
I. Souza, J. Iniguez and D. Vanderbilt, Phys. Rev. Lett. 89, 117602 (2002).
P. Umari and A. Pasquarello, Phys. Rev. Lett. 89, 157602 (2002).
DFPT in E-field
X. Wang and D. Vanderbilt, in preparation.
N. Sai, K.M. Rabe, and D. Vanderbilt, Phys. Rev. B 66, 104108 (2002).
O. Dieguez and D. Vanderbilt, in preparation.
Systematic DFPT for E-fields and strain
X. Wu, D. Vanderbilt, and D.R. Hamann, submitted to Physical Review B.
D.R. Hamann, X. Wu, K.M. Rabe, and D. Vanderbilt, and, Phys. Rev. B. 71, 035117 (2005).

Introduction
Context: DFT (density functional theory)

By mid-1990s, linear-response (DFPT)
allowed calculation of:
Response of P to any perturbation
Response of anything to E-field perturbation
However, it was not known how to:
Calculate P itself
Treat finite E-fields

Introduction
Solutions of these problems are now in hand

Modern theory of polarization (1993)
Treatment of finite E-fields (2002)
Allows routine calculation of non-linear dielectric,
piezoelectric properties of complex materials
This talk:
Emphasis is on methods!
Touch only very briefly on
applications

Theory of electric polarization
Electric polarization:
P = d / volume
How to define as a bulk quantity?
a) P = dsample / Vsample ?
b) P = dcell / Vcell ?
c) P Snk ynkrynk ?

P = dsample / Vsample ?
L x L x L sample:
-s +s
DP = ( L2 s ) . L / L3

P = d / volume
c) P Snk ynkrynk ?

P = dcell / Vcell ?
Textbook picture
+ + + (Claussius-Mossotti)
But does not correspond
to reality!
+ + +


Ferroelectric PbTiO3 (Courtesy N. Marzari)
P = dcell / Vcell ?
dcell = 0

P = dcell / Vcell ?
dcell =

P = dcell / Vcell ?
dcell =

P = d / volume
c) P Snk ynkrynk ?

P = d / volume
c) P Snk ynkrynk ?

P = d / volume
c) P Snk ynkrynk ?
d) P Snk unkikunk ?
Attempt 4

Simplify: 1 band, 1D

Discrete sampling of k-space

Gauge invariance

Discretized formula in 3D
where

Sample Application: Born Z*
+2 e ?
+4 e ?
2e ?
2e ?
Paraelectric Ferroelectric

Outline
Introduction
Electric fields
Wannier functions

Electric Fields: The Problem
Easy to do in practice:
But ill-defined in principle:

Zener
tunneling
For small E-fields, tZener >> tUniverse ; is it OK?

Electric Fields: The Problem
y(x) is very
messy is not periodic
Blochs theorem does not apply
acts as singular perturbation
on eigenfunctions
not bounded from below
There is no ground state

Electric Fields: The Solution
Seek long-lived resonance

Described by Bloch functions
Minimizing the electric enthalpy functional
(Nunes and Gonze, 2001)
Usual EKS
Berry phase polarization
Justification?

Electric Fields: Justification
Seek
long-lived
metastable
periodic
solution

Electric Fields: The Hitch
There is a hitch!
For given E-field, there is a limit on k-point sampling
Length scale LC = 1/Dk
Meaning: LC = supercell dimension
Nk = 8
L c = 8a
Solution: Keep Dk > 1/Lt = e/Eg

Can check that previous results

for BaTiO3 are reproduced

(Souza,Iniguez,
and Vanderbilt,
2002)

Outline
Introduction
Electric fields
Wannier functions

Wannier function representation
(Marzari and
Vanderbilt, 1997)
Wannier center
Mapping to Wannier centers
Wannier
center
rn

Mapping to Wannier centers
Wannier dipole theorem
DP = Sion (Zione) Drion

+ Swf ( 2e) Drwf
Exact!
Gives local description of
dielectric response!

Ferroelectric BaTiO3 (Courtesy N. Marzari)
Wannier functions Wannier functions
in a-Si in l-H2O
Fornari et al. Silvestrelli et al.

Wannier analysis of PVDF polymers and copolymers
S. Nakhmanson et al. (W26.3 2:54pm Thursday)

Outline
Introduction
Electric fields
Wannier functions

Systematic treatment of E-fields and strain
(X. Wu, D. Vanderbilt, and D.R. Hamann, submitted to PRB)
We identify six needed elementary tensors:

cab = Frozen - ion dielectric tensor
C jk = Frozen - ion elastic tnsor
K mn = Force - constant matrix
Z ma = Dynamical effective charge tensor
L mj = Internal strain tensor
eaj = Frozen - ion piezoelectric tensor
These are computed within ABINIT using DFPT methods.

What are they?

They are elements of big Hessian matrix
Displacement Strain E -field
K -L -Z
Displacement
Strain -L C -e
E - field
-Z -e c

Build from To
Elementary Tensors Relaxed-ion tensors
K mn
cab c ab
C jk
C jk
Z ma
eaj
L mj
eaj

Use relaxed ion cab , C jk , eaj to compute
C (jkD ) = C (jke ) + eaj bab

(h )
ebk Elastic tensor at fixed D
(s )
cab = cab + eaj (C -1 ) jk ebk Free-stress dielectric tensor
S jk = (C -1 ) jk Elastic compliance tensor
b (h ) = (e (h ) )( -1) Inverse dielectric tensor
daj = S (jke ) eak
(s )
g aj = bab d bj Various piezoelectric tensors
(h )
haj = bab ebj
d aj
kaj = Electromechanical coupling
(s ) (e )
s aa
S jj

Elastic tensors at different elec. BCs: ZnO
C(e) (GPa)
226 139 123 0 0 0 Apply strain perturbation
Metallic
139 226 123 0 0 0
123 123 242 0 0 0 Short circuit
boundary condition
0 0 0 40 0 0
0 0 0 0 40 0
Metallic
0 0 0 0 0 44
Measuring stress response and get C(e)
C(D) (GPa)
231 144 114 0 0 0 Apply strain perturbation
Metallic
144 231 114 0 0 0
Open circuit
114 114 260 0 0 0 boundary condition
0 0 0 43 0 0
0 0 0 0 43 0
Metallic
0 0 0 0 0 44
Measuring stress response and get C(D)
Outline
Introduction
Electric fields
Wannier functions

Mapping Energy vs. Polarization
BaTiO3
Conference Dieguez
Oswaldo on Computational
(W26.7 Physics,
3:42pmLos Angeles, 2005
Thursday)
Status of Implementation in Code Packages
All major codes: ABINIT, PWSCF, VASP, CPMD, SIESTA, CRYSTAL, etc.
Electric fields
ABINIT (courtesy I. Souza, J. Iniguez, M. Veithen)
Maximally localized Wannier functions:
Package at www.wannier.org (courtesy N. Marzari)
ABINIT (courtesy X. Wu, D.R. Hamann, K. Rabe)
DFPT in finite electric field
Coming to ABINIT soon (courtesy X. Wang)
Mapping energy vs. P
Coming to ABINIT soon (courtesy O. Dieguez)

Summary and Prospects
Problem and solution
Electric fields
Problem and solution
Wannier functions
New directions:
Dynamic generalizations of Pberry
(I. Souza, Valley Prize Talk, B3.1 11:15am Monday)
DFPT in finite electric field
(X. Wang, S32.3 2:30pm Wednesday)
Many possible applications


Insulators, polarization, and electric fields from first principles

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Polarization, electric fields, and

dielectric response in insulators

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Context: DFT (density functional theory)

Conference on Computational Physics, Los Angeles, 2005

Solutions of these problems are now in hand

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

But ill-defined in principle:

For small E-fields, tZener >> tUniverse ; is it OK?

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Seek long-lived resonance

(Nunes and Gonze, 2001)

Berry phase polarization

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Solution: Keep Dk > 1/Lt = e/Eg

Can check that previous results

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Wannier dipole theorem

DP = Sion (Zione) Drion

Conference on Computational Physics, Los Angeles, 2005

Fornari et al. Silvestrelli et al.

S. Nakhmanson et al. (W26.3 2:54pm Thursday)

Conference on Computational Physics, Los Angeles, 2005

(X. Wu, D. Vanderbilt, and D.R. Hamann, submitted to PRB)

We identify six needed elementary tensors:

These are computed within ABINIT using DFPT methods.

Conference on Computational Physics, Los Angeles, 2005

Displacement Strain E -field

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

C (jkD ) = C (jke ) + eaj bab

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

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