Polarization Integration

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

Principal References
Polarization

R.D. King-Smith and D. Vanderbilt, Phys. Rev. B 47, 1651 (1993). R. Resta, Rev. Mod. Phys. 66, 899 (1994). I. Souza, J. Iniguez and D. Vanderbilt, Phys. Rev. B 69, 085106 (2004). 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). 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. 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).
Review on polarization Dynamics of polarization Finite electric field
DFPT in E-field

Mapping energy vs. polarization Systematic DFPT for E-fields and strain

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 = 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 =

a) b) c) d)
P P P P
= dsample / Vsample ? = dcell / Vcell ? Snk ynkrynk ? 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 ?
Paraelectric Ferroelectric
2e ?

Outline
Electric fields
Wannier functions

Mapping energy vs. polarization Systematic treatment of E-fields and strains

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
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 in a-Si
Wannier functions 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
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 Displacement Strain E - field E -field
K -L -Z
-L C -e
-Z -e

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

Use relaxed ion cab , C jk , eaj to compute

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

Elastic tensors at different elec. BCs: ZnO

C(e) (GPa)
226 139 123 0 0 0 139 226 123 0 0 0 123 123 242 0 0 0 0 0 0 40 0 0 0 0 0 0 40 0 0 0 0 0 0 44
Metallic
Apply strain perturbation Short circuit boundary condition
Metallic Measuring stress response and get
C(D) (GPa)
231 144 114 0 0 0 144 231 114 0 0 0 114 114 260 0 0 0 0 0 0 43 0 0 0 0 0 0 43 0 0 0 0 0 0 44
C(e)
Metallic
Apply strain perturbation Open circuit boundary condition
Metallic Measuring stress response and get
C(D)

Outline
Electric fields
Wannier functions


Mapping Energy vs. Polarization
BaTiO3
Conference on Computational Physics, Los Angeles, 2005 Oswaldo Dieguez (W26.7 3:42pm Thursday)
Status of Implementation in Code Packages

Electric polarization
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)
Systematic treatment of E-fields and strains

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

Electric polarization
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


Polarization Integration

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Polarization, electric fields, and dielectric response in insulators

David Vanderbilt Rutgers University

Conference on Computational Physics, Los Angeles, 2005

Dielectric and piezoelectric properties

Summary and prospects

Mapping E vs. P Systematic DFPT in E and strain DFPT in presence of E-field

Conference on Computational Physics, Los Angeles, 2005

Review on polarization Dynamics of polarization Finite electric field

Conference on Computational Physics, Los Angeles, 2005

However, it was not known how to:

Conference on Computational Physics, Los Angeles, 2005

Allows routine calculation of non-linear dielectric, piezoelectric properties of complex materials

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

= dsample / Vsample ? = dcell / Vcell ? Snk ynkrynk ? Snk unkikunk ?

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Discrete sampling of k-space

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Conference on Computational Physics, Los Angeles, 2005

Sample Application: Born Z*

Conference on Computational Physics, Los Angeles, 2005

Dielectric and piezoelectric properties

Summary and prospects

Electric Fields: The Problem

But ill-defined in principle:

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

Electric Fields: The Problem

Conference on Computational Physics, Los Angeles, 2005

Electric Fields: The Solution

Usual EKS Berry phase polarization

Electric Fields: Justification

Seek long-lived metastable periodic solution

Conference on Computational Physics, Los Angeles, 2005

Electric Fields: The Hitch

Solution: Keep Dk > 1/Lt =

Conference on Computational Physics, Los Angeles, 2005

Sample Application: Born Z*

Can check that previous results for BaTiO3 are reproduced

Sample Application: Born Z*

(Souza,Iniguez, and Vanderbilt, 2002)

Conference on Computational Physics, Los Angeles, 2005

Dielectric and piezoelectric properties

Summary and prospects

Wannier function representation

(Marzari and Vanderbilt, 1997)

Mapping to Wannier centers

Conference on Computational Physics, Los Angeles, 2005

Mapping to Wannier centers

Sion (Zione) Drion + Swf ( 2e) Drwf

Exact! Gives local description of dielectric response!

Wannier functions in a-Si

Wannier functions in l-H2O

Wannier analysis of PVDF polymers and copolymers

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

Dielectric and piezoelectric properties

Summary and prospects

Conference on Computational Physics, Los Angeles, 2005