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Localized Electrons with Wien2k

LDA+U, EECE, MLWF, DMFT

Elias Assmann
Vienna University of Technology, Institute for Solid State Physics WIEN2013@PSU, Aug 14

LDA vs. Localized Electrons

LDA/GGA has problems with strongly correlated systems


localized orbitals (3d, 4f )

explicitly add Coulomb interaction


1

LDA+U, EECE: add orbital-dependent potentials to LDA


insulators

DMFT: build many-body theory on top of LDA


correlated metals partially-lled bands Wannier functions as basis

The Hubbard Model


single-band Hubbard model: t H = t
i j

ci cj + U
i

ni ni

U
hopping t (kinetic energy) interaction U

The Hubbard Model


single-band Hubbard model: t H = t
i j

ci cj + U
i

ni ni

U
hopping t (kinetic energy) interaction U

multi-band generalization: U n n
ijkl

Uijkl ci cj cl ck

+ +

often parametrized with: intra-orbital U, inter-orbital V , Hund exchange J

Strontium Vanadate SrVO3


correlated metal cubic perovskite
VO octahedra 6

isolated t 1 manifold 2g

DOS

-5

0 [eV]

10

Outline

Preliminaries LDA+U, EECE Orbital-Dependent Potentials LDA + Coulomb Repulsion U On-Site Hybrid/Hartree-Fock Wannier Functions and DMFT

LDA + Coulomb Repulsion U (-orb)


split states into
delocalized LDA localized LDA+U (usually, d or f states)

augment LDA with local orbital-dependent energy:

E = ELDA +

1 U 2 i=j

ni nj

1 U N(N 1) 2

mean-eld Hubbard term (multi-band) ni ni = ni

double-counting correction (LDA contains part of U)

[Anisimov et al., Phys. Rev. B 48, 16929 (1993)]

LDA+U: Effects

E = ELDA + 1 U 2
i=j

1 ni nj 2 U N(N 1)

orbital energies i =

E ni

= LDA + U (1/ 2 ni ) i

unoccupied states , occupied states


creates / enlarges gaps ( breaks symmetries (

Mott insulators)

spin order, orbital order, . . . )

LDA+U: Practicalities
conceptually simple, computationally cheap ambiguities in practice: U values?
constrained LDA
enforce occupation of target orbital U Etot
[Madsen and Novk, wien2k.at]

double-counting correction
1 ) 0 around mean-eld, 2 UN(N n metallic or less strongly correlated [Czy zyk and Sawatzky, PRB 1994]

1 self-interaction correction, strongly correlated systems 2 HMF

1 UN(N 1) 2

[Anisimov et al., PRB 1993]

[Anisimov et al., PRB 1991]

LDA+U: Program Flow


must be spin-polarized

runsp -orb
lapw0 orb lapw1 -orb lapw2 lapwdm lcore mixer -orb -up,dn -up,dn -up,dn -up,dn -up,dn

lapwdm density matrix nij = ni nj (case.dmatup,dn) orb LDA+U potential (case.vorbup,dn) lapw1 -orb includes LDA+U potential

LDA+U: Program Flow


must be spin-polarized

runsp -orb
lapw0 orb lapw1 -orb lapw2 lapwdm lcore mixer -orb -up,dn -up,dn -up,dn -up,dn -up,dn

lapwdm density matrix nij = ni nj (case.dmatup,dn) orb LDA+U potential (case.vorbup,dn) lapw1 -orb includes LDA+U potential

case.indm[c]
-9. 1 2 1 0 0 2 Emin [Ry] #atoms atom, #l, l mode

case.inorb
1 1 0 mode, #atoms, ipr PRATT 1.0 mixing 2 1 2 atom, #l, l 1 double-counting 0.26 0.00 U,J [Ry] (Ueff=U-J)

LDA+U: SrVO3
LDA LDA+U t2g

DOS

-5

0 [eV]

10

On-Site Hybrid Functionals (-eece)


split states as in LDA+U sel , sel Whats in a name?
exact exchange for correlated electrons on-site hybrid/Hartree-Fock vs. full hybrid

augment LDA with local orbital-dependent energy:


on-site hybrid

E = ELDA [] + EHF [sel ] ELDA [sel ]) x x


on-site Hartree-Fock

E = ELDA [] + (EHF [sel ] ELDA [sel ]) x xc

must choose ; Exc [] is not linear


[Novk et al. Phys. Stat. Sol. B 243, 563 (2006)] [Tran, Blaha, Schwarz, and Novk, Phys. Rev. B 74, 155108 (2006)]

EECE: Program Flow


runsp -eece
must be spin-polarized

lapwdm density matrix nij = ni nj (case.dmatup,dn) lapw2, lapw0, orb EECE potential (case.vorbup,dn) lapw1 -orb includes EECE potential

lapw0 lapw1 -orb lapw2 lcore lapwdm lapw2 -eece lapw0 -eece orb mixer -eece

-up,dn -up,dn -up,dn -up,dn -up,dn -up,dn

EECE: Program Flow


runsp -eece
must be spin-polarized

lapwdm density matrix nij = ni nj (case.dmatup,dn) lapw2, lapw0, orb EECE potential (case.vorbup,dn) lapw1 -orb includes EECE potential

lapw0 lapw1 -orb lapw2 lcore lapwdm lapw2 -eece lapw0 -eece orb mixer -eece

-up,dn -up,dn -up,dn -up,dn -up,dn -up,dn

case.ineece
-9.0 2 1 HYBR 0.25 1 2 Emin [Ry], #atoms iatom nlorb lorb HYBR/EECE mode

case.inorb, case.indm[c]
(generated automatically)

EECE: SrVO3
LDA EECE t2g

DOS

-5

0 [eV]

10

Outline

Preliminaries LDA+U, EECE Orbital-Dependent Potentials Wannier Functions and DMFT Maximally Localized Wannier Functions Wannier90 Wien2Wannier Dynamical Mean-Field Theory at a Glance

Wannier Functions
Fourier transforms of

Bloch functions: |w nR = (2V )3


BZ

dk eikR | nk

from Marzari et al.

Wannier Functions
Fourier transforms of

Bloch functions: |w nR = (2V )3


BZ

dk eikR | nk

gauge freedom:

| w nR =
V (2 ) BZ
from Marzari et al.

dk
m

eikR Umn (k ) | mk

choose U(k ) to minimize spread r 2

Maximally Localized Wannier Functions

choose U(k ) to minimize spread

MLWF

total spread = I + can be split into

gauge-invariant part and rest minimize


wannier90 computes U(k ) in this way
[Marzari et al., Rev. Mod. Phys. 84, 1419 (2012)] http://wannier.org

wien2wannier provides interface to Wien2k


[Kune s, Wissgott et al., Comp. Phys. Commun. 181, 1888] http://www.wien2k.at/reg_user/unsupported/wien2wannier/

Disentanglement

other bands may cross

target manifold must select bands to Wannierize


V (k ) J(k ) N

from Marzari et al.

selection determines I

fcc-Cu, 5 d-like WF, 2 interstitial s-like WF num_bands = 12 num_wann = 7

minimize also I

MLWF: Applications

analysis of chemical bonding electric polarization and orbital magnetization


Oleg Rubels talk (tomorrow, 10:30)

Wannier interpolation K G

H(k )|K H(R)|K1 H(k )|G


Wannier functions as basis functions
tight-binding model H(k ) = U+ (k ) (k ) U(k )

F 1

realistic dynamical mean-eld theory (DMFT)

wannier90
case.win
num_bands num_wann num_iter num_print_cycles dis_froz_min dis_froz_max = 3 = 3 = 1000 = 100 = 7. = 9.

case.wout
Final State WF centre and spread 1 WF centre and spread 2 WF centre and spread 3 Sum of centres and spread ... ... ... ...

bands_plot_project = 1

[Marzari et al., Rev. Mod. Phys. 84, 1419 (2012)] http://wannier.org

wien2wannier
case.w2win
BOTH 21 3 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 23 3 -2 2 -1 1 -1 1 min band, max band LJMAX, #Wannier functions #terms 0.00000000 0.70710677 atom, L, M, coeff 0.00000000 -0.70710677 0.00000000 0.00000000 0.70710677 -0.70710677 0.70710677 0.70710677 0.00000000 0.00000000

[Kune s, Wissgott et al., Comp. Phys. Commun. 181, 1888] http://www.wien2k.at/reg_user/unsupported/wien2wannier/

MLWF: Program FLow

normal SCF run converged density, band structure prepare_w2wdir.sh, init_w2w: prepare input les x lapw1 -options eigenvectors on full k-mesh w2w case overlap umk |unk shift_energy case wannier90.x case U(k )

wien2wannier Features
spin-polarized cases, spin-orbit coupling any functional, LAPW, APW+LO basis disentanglement plotting: interface to XCrysDen / VESTA woptic: optical conductivity with Wannier functions

()
k ,

f ()f (+)

tr VA(k , + )VA(k , )

adaptive k-integration includes self-energy

() (DMFT)

http://www.wien2k.at/reg_user/unsupported/wien2wannier/ [Wissgott, Kune s et al. Phys. Rev. B 85, 205133]

LDA+DMFT
LDA
realistic calculations fails for strong correlations

model Hamiltonians
simplied, abstract model full correlations

LDA+DMFT
LDA
realistic calculations fails for strong correlations

model Hamiltonians
simplied, abstract model full correlations

LDA+DMFT
realistic calculation including most important correlation effects
Held, Adv. Phys. 56, 829 (2007) Kotliar et al., Rev. Mod. Phys. 78, 865 (2006)

Correlation Regimes

U: screened local interaction

W : bandwidth, t

From lattice models to DMFT


U U t U U U U

lattice model
e hop between sites local repulsion (screened)

From lattice models to DMFT


U U t U U U U U

lattice model
e

impurity model
one interacting site non-interacting bath

hop between sites

local repulsion (screened)

From lattice models to DMFT


U U t U U U U DMFT U

lattice model
e

impurity model
one interacting site non-interacting bath

hop between sites

local repulsion (screened)

dynamical mean-eld theory


lattice model impurity model self-energy ()
Georges et al., RMP 1996, Kotliar & Vollhardt, Phys. Today 2004

LDA+DMFT for SrVO3


DMFT basis: 3 degenerate t2g Wannier functions U = 5.05 eV, T = 1160 K
DMFT(QMC) has nite T low T is hard (sign problem)

experiment: Makino et al., PRB 58, 4348 (1997) DMFT: Philipp Wissgott

LDA+U, EECE, DMFT compared


LDA+U, EECE
density functionals
single-particle model

double counting semi-empirical U,

good for insulators (U work inside MT sphere

W)

basis: Ylm
computationally cheap

LDA+DMFT
spectral density functional theory
many-body physics

double counting semi-empirical U

basis: Wannier functions

(or similar)
whole U/ W range sophisticated, expensive