Mssbauer parameters from DFT-based WIEN2k calculations for extended systems

Peter Blaha
Institute of Materials Chemistry

TU Vienna

Main Mssbauer parameters:

The main (conventional) Mssbauer spectroscopy parameters which we want to calculate by theory are: Isomer shift: = (0Sample 0Reference);

it is proportional to the electron density 0 at the nucleus the constant is proportional to the change of nuclear radii during the transition (we use =-.291 au3mm s-1)

Magnetic Hyperfine fields: Btot = Bcontact + Borb + Bdip

these fields are proportional to the spin-density at the nucleus and the orbital moment of the probed atom as well as the spin moment distribution in the crystal

Quadrupole splitting:

e Q Vzz

given by the product of the nuclear quadrupole moment Q times the electric field gradient Vzz. The EFG is proportional to an integral over the non-spherical charge density (weighted by 1/r 3)

Schrdinger equation

From the previous slide it is obvious, that we need an accurate knowledge of the electron (and magnetization) density, which in principle can be obtained from the solution of the many-body Schrdinger equation in the corresponding solid.

H=E

However, a many-body problem with ~1023 particles is not solvable at all and we must create models for the real material and rely on an approximate solution of the Schrdinger equation. (This will be briefly discussed in the
next slides and my preferred options are marked in red.)

Concepts when solving Schrdingersequation

Non-spinpolarized Spin polarized (with certain magnetic order)

Treatment of spin

Form of potential

Muffin-tin MT atomic sphere approximation (ASA) pseudopotential (PP) Full potential : FP

Relativistic treatment of the electrons

non relativistic semi-relativistic fully-relativistic

exchange and correlation potential

Hartree-Fock (+correlations) Density functional theory (DFT) Local density approximation (LDA) Generalized gradient approximation (GGA) Beyond LDA: e.g. LDA+U

1 2 k k k Schrdinger - equation + V ( r ) = i i i 2
Representation of solid Basis functions
plane waves : PW augmented plane waves : APW atomic oribtals. e.g. Slater (STO), Gaussians (GTO), LMTO, numerical basis

non periodic (cluster, individual MOs) periodic (unit cell, Blochfunctions, bandstructure)

Representation of the solid

cluster model: approximate the solid by a finite (small) number of atoms. This can be a
good approximation for molecular crystals.

periodic model:
use a unit cell, which is repeated infinitely. This approximates the real solid (finite with surfaces, imperfect) by an infinite ideal solid. with supercells also surfaces, vacancies or impurities can be modelled.

BaSnO3

SnS

Exchange and correlation

The electron-electron interaction can be approximated by: Hartree-Fock
exact exchange, but no correlation at all (in solids often very important !) correlation can approximately be added at various levels: MP2, CC, CI, ... HF (and even more adding correlation) is very expensive in solids.

Density functional theory:

the exact functional is unknown, thus one must approximate exchange + correlation. Fast method, fairly accurate in solids. LDA: local density approximation, free electron gas GGA: generalized gradient approximation, various functionals hybrid-DFT: mixing of HF + GGA, various functionals LDA+U, DMFT: explicit (heuristic) inclusion of correlations a brief summary of DFT follows

DFT Density Functional Theory

Hohenberg-Kohn theorem: (exact)
The total energy of an interacting inhomogeneous electron gas in the presence of an external potential Vext(r ) is a functional of the density

E = Vext ( r ) ( r )dr + F [ ]

This (exact) statement states, that we need to know only the electron density , but we do NOT need to know the wavefunctions (solution of Schrdinger equation not necessary). However, the exact functional form of F[] is unknown and any approximation so far is too crude.

DFT - Kohn Sham (still exact)

Lets decompose the total functional F[] into parts which can be calculated exactly and some unknown, but small rest: 1 ( r ) ( r ) E = To [ ] + Vext ( r )d r + dr dr + E xc [ ] 2 | r r | Ekinetic Ene Ecoulomb Eee Exc exchangenon interacting

correlation

Ekinetic is the kinetic energy of non-interacting particles Ecoulomb is the classical electrostatic interaction between electrons (including the self-interaction energy) Exc is the exchange-correlation energy and should correct for the self-interaction and approx. kinetic energy The exact Exc is again unknown, but now an approximation for the small correction may be accurate enough.

Kohn-Sham equations
1 ( r ) ( r ) E = To [ ] + Vext ( r )d r + dr dr + E xc [ ] 2 | r r |

vary

1 2 { + Vext ( r ) + VC ( ( r )) + V xc ( ( r ))} i ( r ) = i i ( r ) 2
-Z/r

1-electron equations (Kohn Sham)

(r ) dr |r r |
E xc ( )

(r ) =

i EF

2 | | i

Exc and Vxc are unknown and must be approximated LDA or GGA
treat both, exchange and correlation effects approximately

Walter Kohn, Nobel Prize 1998

Chemistry

Approximations to EXC

Local density approximation (LDA):

E

LDA xc

(r)

hom . xc

[ ( r )] dr

(r)

dr

xc is the exchange-correlation energy density of the homogeneous electron gas at density .

Second order gradient expansion (GEA):

E

GEA xc

=E

LDA xc

+ C ( ) (r)
,

( r ) dr

The GEA XC-hole nXC(r,r) is not a hole of any physical system and violates

nX(r,r) 0 nX(r,r) dx = -1 nC(r,r) dx = 0

exchange hole must be negative must contain charge -1 e-

at r

nXC(r,r)

Generalized gradient approximations (GGA)

GGA E xc ( r ) F [ ( r ), ( r )] dr

construct GGAs

by obeying as many known constraints as possible ( Perdew)

recover LDA for slowly varying densities obey sum rules and properties of XC-holes long range limits: lim(r -> ): exc=-1/2r ; vxc=C-1/r scaling relations Lieb-Oxford bound

fitting some parameters to recover exact energies of small systems (set of small molecules) or lattice parameters in solids (Becke, Handy, Hammer, ..) well balanced GGA; equally bad for all systems

Perdew-Burke-Enzerhof GGA (PRL 1996):

better approximations are constantly developed

meta-GGAs:
Perdew,Kurth,Zupan,Blaha (PRL 1999):
m GGA E xc ( r ) F [ ( r ), ( r ), 2 ( r ), ( r )] dr

1 2 use laplacian of , or the kinetic energy density ( r ) = i ( r ) 2 i

analytic form for Vxc not possible (Vxc = dExc/dr) , SCF very difficult

better meta-GGAs under constant development

more non-local functionals (beyond LDA)

Self-Interaction correction (Perdew,Zunger 1981; Svane+ Temmermann)

vanishes for Bloch-states, select localized states by hand

LDA+U, DMFT (dynamical mean field theory)

approximate HF for selected highly-correlated electrons (3d,4f,5f) empirical parameter U

Exact exchange (similar to HF but DFT based, misses correlation) Hybrid functionals (mixing of LDA (GGA) + HF)

DFT ground state of iron

LSDA

NM fcc in contrast to experiment

GGA

LSD A

GGA

GGA

FM bcc Correct lattice constant FM bcc

Experiment

LSDA

A: Fe is nonmagnetic and in fcc structure A correctly predicts Fe to be ferromagnetic and in bcc struct

Everybody in Austria knows about the importance of DFT

The 75th GGA-version follows the 52nd LDAversion

(thanks to Claudia Ambrosch (TU Leoben))

basis set for the wave functions

Even with an approximate e--e- interaction the Schrdinger equation cannot be solved exactly, but we must expand the wave function into a basis set and rely on the variational principle. quantum chemistry: LCAO methods
Gauss functions (large experience for many atoms, wrong asymptotic, basis set for heavier atoms very large and problematic, .. ) Slater orbitals (correct r~0 and r~ asymptotic, expensive) numerical atomic orbitals

physics: plane wave (PW) based methods

plane waves + pseudo-potential (PP) approximation
PP allow fast solutions for total energies, but not for Hyperfine parameters

augmented plane wave methods (APW)

spatial decomposition of space with two different basis sets: combination of PW (unbiased+flexible in interstitial regions) + numerical basis functions (accurate in the atomic regions, correct cusp)

Computational approximations
relativistic treatment: non- or scalar-relativistic approximation (neglects spin-orbit, but includes Darvin s-shift and mass-velocity terms) adding spin-orbit in second variation (good enough) fully-relativistic treatment (Dirac-equation, very expensive) point- or finite-nucleus restricted/unrestricted treatment of spin use correct long range magnetic order (FM, AFM) approximations to the form of the potential shape approximations (ASA) pseudopotential (smooth, nodeless valence orbitals) full potential (no approximation)

Concepts when solving Schrdingersequation in many cases, the experimental knowledge about a certain system is very limited and also the exact atomic positions may not be known accurately (powder samples, impurities, surfaces, ...) Thus we need a theoretical method which can not only calculate HFFparameters, but can also model the sample: total energies + forces on the atoms: perform structure optimization for real systems calculate phonons investigate various magnetic structures, exchange interactions electronic structure: bandstructure + DOS compare with ARPES, XANES, XES, EELS, ... hyperfine parameters isomer shifts, hyperfine fields, electric field gradients

WIEN2k software package

An Augmented Plane Wave Plus Local Orbital Program for Calculating Crystal Properties

Peter Blaha Karlheinz Schwarz Georg Madsen Dieter Kvasnicka Joachim Luitz
November 2001 Vienna, AUSTRIA Vienna University of Technology

WIEN2k: ~1530 groups mailinglist: 1800 users

http://www.wien2k.at

APW based schemes

APW (J.C.Slater 1937)

Non-linear eigenvalue problem Computationally very demanding Generalized eigenvalue problem Full-potential (A. Freeman et al.) treatment of semi-core states (avoids ghostbands) Efficience of APW + convenience of LAPW Basis for
K.Schwarz, P.Blaha, G.K.H.Madsen, Comp.Phys.Commun.147, 71-76 (2002)

LAPW (O.K.Andersen 1975)

Local orbitals (D.J.Singh 1991)

APW+lo (E.Sjstedt, L.Nordstrm, D.J.Singh 2000)

APW Augmented Plane Wave method

The unit cell is partitioned into: atomic spheres Interstitial region unit cell

Rmt

rI

Basisset: i ( k + K ). r PW:

Atomic partial waves K

join

A
m

) u ( r , )Ym ( r

ul(r,) are the numerical solutions of the radial Schrdinger equation in a given spherical potential for a particular energy AlmK coefficients for matching the PW

Slaters APW (1937)

Atomic partial waves
K A mu(r, )Ym (r) m

Energy dependent basis functions lead to H Hamiltonian S overlap matrix Non-linear eigenvalue problem

One had to numerically search for the energy, for which the det|H-ES| vanishes. Computationally very demanding.

Linearization of energy dependence

LAPW suggested by
antibonding center bonding

O.K.Anderse n,
Phys.Rev. B 12, 3060 (1975)
m

( E , r )]Ym ( r ) [ Am ( k n )u ( E , r ) +Bm ( k n )u k n =

expand ul at fixed energy El

l = u and add

ul /

Atomic sphere

Almk, Blmk: join PWs in value and slope General eigenvalue problem (diagonalization) additional constraint requires more PWs than APW

LAPW APW

PW

Full-potential in LAPW
etal.)

(A.Freeman

SrTiO3

The potential (and charge density) can be of general form (no shape approximation)

V (r ) =
Full potential

{
LM K

) VLM (r )YLM ( r VK e
iK . r

r < R

rI

Inside each atomic sphere a local coordinate system is used (defining LM)

Muffin tin
approximation

TiO2

Ti

Problems of the LAPW method

LAPW can only treat ONE principle quantum number per l. Problems with high-lying semi-core states

Extending the basis: Local orbitals (LO)

E1 E1 E2 ) LO = [ Amu + Bmu + Cmu ]Ym ( r

LO: contains a second ul(E2)

Ti atomic sphere

is confined to an atomic sphere has zero value and slope at R can treat two principal QN n for each azimuthal QN (3p and 4p) corresponding states are strictly orthogonal (no ghostbands) tail of semi-core states can be represented by plane waves only slight increase of basis D.J.Singh, set Phys.Rev. B 43 6388 (1991) (matrix size)

New ideas from Uppsala and Washington E.Sjstedt, L.Nordstrm, D.J.Singh,

An alternative way of linearizing the augmented plane wave method,

Solid State Commun. 114, 15 (2000) Use APW, but at fixed El (superior PW convergence) Linearize with additional lo (add a few basis E E ) = [ A u + B u = A ( k ) u ( E , r ) Y ( r ) lo m m ]Ym ( r k m n m functions)
1 1

optimal solution: mixed basis use APW+lo for states which are difficult to converge: (f or d- states, atoms with small spheres) use LAPW+LO for all other atoms and basis for

Relativistic treatment
For example:

Ti

Valence states

Scalar relativistic

mass-velocity Darwin s-shift

Spin orbit coupling on demand by second variational treatment

Semi-core states

Scalar relativistic on demand

spin orbit coupling by second variational treatment Additional local orbital (see Th6p1/2)

Core states

Fully relativistic

Dirac equation

Relativistic semi-core states in fcc Th

additional local orbitals for 6p1/2 orbital in Th Spin-orbit (2nd variational method)

J.Kune, P.Novak, R.Schmid, P.Blaha, K.Schwarz Phys.Rev.B. 64, 153102 (2001)

Quantum mechanics at work

w2web GUI (graphical user interface)

Structure generator

spacegroup selection import cif file symmetry detection automatic input generation Magnetism (spin-polarization) Spin-orbit coupling Forces (automatic geometry optimization) Energy band structure DOS Electron density X-ray spectra Optics

step by step initialization

SCF calculations

Guided Tasks

An example:

In the following I will demonstrate on one example, which kind of problems you can solve using a DFT simulation with WIEN2k. Of course, also Mssbauer parameters will be calculated and interpreted.

Verwey Transition and Mssbauer Parameters in YBaFe2O5 by DFT calculations Peter Blaha, C. Spiel, K.Schwarz
Institute of Materials Chemistry

TU Wien Thanks to: P.Karen (Univ. Oslo, Norway) C.Spiel, P.B., K.Schwarz, Phys.Rev.B.79, 085104 (2009)

Technical details:

WIEN2k (APW+lo) calculations

WIEN2K
An Augmented Plane Wave Plus Local Orbital Program for Calculating Crystal Properties Peter Blaha Karlheinz Schwarz Georg Madsen Dieter Kvasnicka Joachim Luitz http://www.wien2k.at

Rkmax=7, 100 k-points spin-polarized, various spin-structures + spin-orbit coupling based on density functional theory:

LSDA or GGA (PBE)

Exc Exc(, )

description of highly correlated electrons using non-local (orbital dep.) functionals

LDA+U, GGA+U hybrid-DFT (only for correlated electrons)

mixing exact exchange (HF) + GGA

Verwey-transition:
(1939)

E.Verwey, Nature 144, 327

Fe3O4, magnetite phase transition between a mixed-valence

2 Fe2.5+ Fe2+ + Fe3+
cubic inverse spinel structure AB2O4

and a charge-ordered configuration with tem

Fe2+A (Fe3+,Fe3+)B O4 Fe3+A (Fe2+,Fe3+)B O4

B A
small, but complicated coupling between lattice and charge

Double-cell perovskites: RBaFe2O5

ABO3

O-deficient double-perovskit
Ba

Y (R)

square pyramida coordination

Antiferromagnet with a 2 step Verwey transition around 300

Woodward&Karen, Inorganic Chemistry 42, 1121 (2003)

experimental facts: structural changes in YBaFe2O5

above TN (~430 K): tetragonal (P4/mmm)
430K: slight orthorhombic distortion (Pmmm) due to AFM all Fe in class-III mixed valence state +2.5; ~334K: dynamic charge order transition into class-II MV state, visible in calorimetry and Mssbauer, but not with X-rays 308K: complete charge order into class-I MV state (Fe2+ + Fe3+) large structural changes (Pmma) due to Jahn-Teller distortion; change of magnetic ordering: direct AFM Fe-Fe coupling vs. FM Fe-Fe exchange above TV

structural changes
charge ordered (CO) phase: phase:
Pmma a:b:c=2.09:1:1.96 (20K) (340K)
c

valence mixed (VM)

Pmmm a:b:c=1.003:1:1.93

b a

Fe2+ and Fe3+ form chains along b contradicts Anderson charge-ordering conditions with minimal

antiferromagnetic structure
CO phase: G-type AFM

VM phase:
AFM for all Fe-O-Fe FM across Y-layer (direct Fe-Fe

AFM arrangement in all directions, superexchange paths also across Y-layer exchange) Fe moments in b-direction

4 8 independent Fe atoms

results of GGA-calculations:

Metallic behaviour/No bandgap

Fe-dn t2g states not splitted at EF

Fe-eg t2g eg* t2g eg

overestimated covalency between O-p and Fe-eg

Experiment:

Magnetic moments too small

CO: 4.15/3.65 (for Tb), 3.82 (av. for Y) VM: ~3.90

Calculation:

CO: 3.37/3.02 VM: 3.34 no significant charge order

charges of Fe2+ and Fe3+ sites nearly identical

CO phase less stable than VM

LDA/GGA NOT suited for this compound!

Localized electrons: GGA+U

Hybrid-DFT

ExcPBE0 [] = ExcPBE [] + (ExHF[sel] ExPBE[sel]) ELDA+U(,n) = ELDA() + Eorb(n) EDCC()

LDA+U, GGA+U

separate electrons into itinerant (LDA) and localized e- (TM-3d, RE 4f e-) treat them with approximate screened Hartree-Fock correct for double counting

Hubbard-U describes coulomb energy for 2e- at the same site

orbital dependent potential

Vm ,m ', = (U J )( 1 nm,m ', ) 2

Determination of U

Take Ueff as empirical parameter (fit to experiment) or estimate Ueff from constraint LDA calculations

constrain the occupation of certain states (add/subtract e -) switch off any hybridization of these states (core-states) calculate the resulting Etot

we used Ueff=7eV for all calculations

DOS: GGA+U vs. GGA

GGA+U GGA

ngle lower insulator, Hubbard-band t2g band splits in VM splits in CO with Fe 3+ states metallic lower than Fe

insulator

GGA+U

metal

magnetic moments and band gap

magnetic moments in very good agreement with exp.

LDA/GGA: CO: 3.37/3.02

VM: 3.34 B

orbital moments small (but significant for Fe2+) exp: semiconductor (like Ge); VM phase has increased conductivity LDA/GGA: metallic

band gap: smaller for VM than for CO phase

Charge transfer (in GGA+U)

Charges according to Baders Atoms in Molecules theory n = 0

Define an atom as region within a zero flux surface Integrate charge inside this region

Structure optimization (GGA+U)

CO phase:

O2a

O2b

Fe2+: shortest bond in y (O2b) Fe3+: shortest bond in z (O1)

O3 O1 O1

VM phase:

all Fe-O distances similar theory deviates along z !!

Fe-Fe interaction different U ?? finite temp. ??

strong coupling between lattice and electrons !

Fe2+ (3d6)
strong covalency effects in eg and d-xz orbitals

CO

Fe3+ (3d5)

VM Fe2.5+ (3d5.5)

majority-spin fully occupied very localized states at lower energy than Fe 2+

minority-spin states d-xz fully occupied (localized) empty occupied short bond in y short bond in z (missing O) distances in z ??

d-z2 partly FM Fe-Fe;

atsup

cryst

CO phase
Fe2+: d-xz Fe3+: d-x2 O1 and O3: polarized toward Fe3+ Fe: d-z2 Fe-Fe interaction O: symmetric

VM phase

dxz spin density ( up- dn) of CO phase

Fe3+: no contribution Fe2+: dxz weak -bond with O orbital tilting of O3 -

Mssbauer spectroscopy:

Isomer shift: = (0Sample 0Reference); =-0.291 au3mm s-1

proportional to the electron density at the nucleus

Magnetic Hyperfine fields: Btot=Bcontact + Borb + Bdip

Bcontact = 8/3 B [up(0) dn(0)] nucleus

spin-density at the

orbital-moment spin-moment

S(r) is reciprocal of the relativistic mass enhancement

nuclear quadrupole interaction

1 2V (0) ( x) xi x j dx 2 ij xi x j

e ij Q 2h

Nuclei with a nuclear quantum number I1 have an electric quadrupole moment Q, which describes the asphrericity of the nucleus Nuclear quadrupole interaction (NQI) can aid to determine the distribution of the electronic charge surrounding such a nuclear site Experiments

NMR NQR Mssbauer PAC

eQ / h

1 ij = Vij ij 2V 3
2V (0) Vij = xi x j

electric field gradient (EFG)

Electric field gradients (EFG)

EFG traceless tensor

1 ij = Vij ij 2V 3
2V (0) Vij = xi x j

with V xx + V yy + Vzz = 0
Vaa Vab Vac Vxx 0 0 Vba Vbb Vbc 0 V yy 0 Vca Vcb Vcc 0 0 Vzz
similarity transformation

traceless
|Vzz| Vxx|

|Vyy| |

/ Vxx / / V yy / / Vzz /

EFG: principal Vzz component asymmetry parameter

0-1 directions of Vxx, Vyy, Vzz

cubic: no EFG; hex, tetragonal (axial symm.): only V zz

theoretical EFG calculations

EFG is tensor of second derivatives of VC at the nucleus:

2V (0) Vij = xi x j

( r) ) Vc ( r ) = dr = VLM ( r )YLM ( r r r LM

Cartesian LM-repr.

Vzz V20 ( r = 0) V yy 1 V20 V22 2 Vxx 1 V20 + V22 2

Vzz
p zz

( r )Y20 p d dr = V + V zz zz r3
p

1 V 3 r 1 V 3 r
d zz

[ 12 ( p [d
xy

+ p y ) pz

] ]

+ d x 2 y 2 1 ( d xz + d yz ) d z 2 2

FG is proportial to differences of orbital occupations

Mssbauer spectroscopy
CO

VM

Isomer shift: charge transfer too small in LDA/GGA

CO

VM

Isomer shifts

= ( 0 0Ref.)

The observed IS is proportional to the charge transfer between the different sites (source and absorber). The 4s (valence) and 3s (semicore) contributions provide 110120% of the effect, and are reduced slightly by opposite 1s,2s contributions. is proportional to the change of nuclear radii during the transition, (in principle a known nuclear constant ). However, a meaningful depends on details of the calculations (we use =-0.291 au3mm s-1):

radial mesh for numerical basis functions (first radial mesh point, RMT) relativistic treatment (NREL, scalar/fully relativistic, point/finite nucleus)

Statements for YBa2Fe2O5

standard LDA/GGA lead to much too small charge transfer and thus the IS are too similar for all 3 Fe sites. need better XCtreatment with increased on-site correlation U , the localization and

Hyperfine fields: Fe2+ has large Borb and Bdip

CO

VM

contact hyperfine fields

The contact HFF dominates in many cases.

It is proportional to the spin-density at the nucleus. B contact = 8/3 B [up(0) dn(0)] It is also proportional to the spin-magnetic moment (but with opposite sign) because the (3d) magnetic moment polarizes the core s-electrons (see below), provided the valence (4s) contribution is small In many cases the core-polarization dominates (the core electrons are polarized due to the 3d magnetic moment):

1s 2s,p 3s,p
3s,p wf.

- 1.4 T - 113.7 T opposite sign; exchange effect with 3s wf. + 60.7 T same sign as 3d moment, strong overlap of 3d and often even smaller, but can be large effects (transferred hyperfine

4s,p + 16.3 T due to ligand total - 38.1 T fields)

Typically, in DFT the contact HFF is about 10-20% too small

Orbital and dipolar - hyperfine fields

Borb is proportional to the orbital moment (an effect due to spin-orbit coupling)

In metals and for high-spin Fe3+ (3d5-up) compounds (closed shell ions) it is usually small. In insulators/semiconductors with partially filled 3d-shells it can be very large (high-spin Fe2+: 3d5-up, 3d1-dn) LDA/GGA usually underestimates this contribution

Bdip is proportional to the anisotropy of the spinmoments around the nucleus

In many cases it is fairly small

EFG: Fe2+ has too small anisotropy in LDA/GGA

CO

VM

theoretical EFG calculations

The coulomb potential Vc is a central quantity in any theoretical calculatio part of the Hamiltonian) and is obtained from all charges (electronic + nuclear) in the system.

(r ) ) Vc (r ) = dr = VLM (r )YLM (r r r LM

he EFG is a tensor of second derivatives of VC at the nucleus:

2V (0) Vij = ; xi x j

(r )Y20 Vzz dr 3 r

ince we use an all-electron method, we have the full charge distributio f all electrons+nuclei and can obtain the EFG without further approxima

he spherical harmonics Y20 projects out the non-spherical (and non-cub art of . The EFG is proportional to the differences in orbital occupations eg. pz vs. px,py)

We do not need any Sternheimer factors

theoretical EFG calculations

(r )Y20 Vzz dr The charge density in the integral 3 r can be decomposed in various ways for analysis:

EF

according to energy (into various valence or semi-core contributions)

according to angular momentum l and m (orbitals) spatial decomposition into atomic spheres and the rest (interstital)

Due to the 1/r3 factor, contributions near the nucleus dominate.

theoretical EFG calculations

We write the charge density and the potential inside the atomic spheres in an lattice-harmonics expansion

) (r ) = LM (r )YLM (r
LM

) V (r ) = vLM (r )YLM (r
LM

spatial decomposition :

(r )Y20 3 Vzz d r = 3 r
Vzz =

sphere

LM

LM

(r )YLM Y20 r3

(r )Y20 3 d r+ d r 3 r int erstital

3

20 (r ) dr + interstitial 3 r sphere

orbital decomposition :

20 (r ) =

nk * nk lm l m 20 k , n.l ,l , m , m

Y dr

p p; d d ; ( s d ) contr.

pp dd Vzz = Vzz + Vzz + ..... + interstitial

theoretical EFG calculations

pp dd Vzz = Vzz + Vzz + ..... + interstitial

V V

pp zz

1 3 r 1 3 r

[ 12 ( p + p ) p ]
x y z

dd zz

[d

1 + d (d xz + d yz ) d z 2 2 2 xy x y 2

EFG is proportial to differences of orbital occupations e.g. between px,py and pz. if these occupancies are the same by symmetry (cubic): Vzz= with axial (hexagonal, tetragonal) symmetry (p x=py): =0 In the following various examples will be presented.

Nuclear Quadrupole moment Q of 56 Fe

Q
FeF2

Compare theoretical and experimental EFGs

1 Q = eQVzz 2

previous value)

FeSi Fe2O3 FeS2 FeCl2 YFe2 Fe4N Fe2P FeZr3 FeNi

FeBr2

(exp.)

testing various DFT approximations: GGA works surprisingly well in FeF2:

LSDA

There is ONE e- in the three Fe d-t2g states. GGA LDA: wrong metallic state, e- is distributed in all 3 orbitals wrong charge density and EFG Fe-EFG in FeF2: GGA splits Fe d-t2g states into a1g and eg LSDA: 6.2 correct charge density and EFG GGA: 16.8

exp:

16.5

EFGs in fluoroaluminates
10 different phases of known structures from CaF 2-AlF3, BaF2-AlF3 binary systems and CaF2-BaF2-AlF3 ternary system Isolated octahedra Isolated chains of octahedra linked by corners Rings formed by four octahedra sharing corners

-BaAlF5 -CaAlF5, -CaAlF5, -BaAlF5, -BaAlF5

-BaCaAlF7 Ca2AlF7, Ba3AlF9-Ib, -Ba3AlF9 Ba3Al2F12

Q and Q calculations using XRD data

performed Q = Attributions 4,712.10 |Vzz | with R = with 0,77 respect to the proportionality -CaAlF
-16 2
5

Q,exp =0,803 Q,cal AlF R2 = 0,38 -CaAlF

3 5

1,8e+6 AlF3 1,6e+6

between |Vzz| and Q for the multi-site compounds

1,0 Ca2AlF7 -BaAlF5 -BaAlF5 -BaAlF5 0,8 Ba3Al2F12 Ba3AlF9-Ib -Ba3AlF9 -BaCaAlF7 Regression Q,mes. =Q, cal.

-CaAlF5 -CaAlF5 Ca2AlF7 -BaAlF5 -BaAlF5 -BaAlF5 Ba3Al2F12 Ba3AlF9-Ib

1,4e+6

Experimental Q (Hz)

1,2e+6

Experimental Q
2,0e+21 3,0e+21
-2

0,6

1,0e+6

-Ba3AlF9 -BaCaAlF7 Rgression

8,0e+5

0,4

6,0e+5

4,0e+5

0,2

2,0e+5

0,0 0,0 1,0e+21

0,0 0,0 0,2 0,4 0,6 0,8 1,0

Calculated Vzz (V.m )

Calculated Q

Important discrepancies when structures are used which were determined from X-ray powder

Q and Q after structure optimization

1,8e+6 1,6e+6

1,4e+6

Q = 5,85.10 Vzz R2 = 0,993

1,0

-16

Q,exp=0,972 Q,cal R2 = 0,983

0,8

Experimental Q (Hz)

1,2e+6

Experimental Q

0,6

1,0e+6

AlF3 -CaAlF5 -CaAlF5 Ca2AlF7

AlF3 -CaAlF5 -CaAlF5 Ca2AlF7 -BaAlF5 -BaAlF5 -BaAlF5 Ba3Al2F12 Ba3AlF9-Ib -Ba3AlF9 -BaCaAlF7 Regression

8,0e+5

0,4

-BaAlF5 -BaAlF5 -BaAlF5 Ba3Al2F12

6,0e+5

4,0e+5

0,2

Ba3AlF9-Ib -Ba3AlF9 -BaCaAlF7 Regression Q,exp. =Q, cal.

2,0e+5

0,0 0,0 5,0e+20 1,0e+21 1,5e+21 2,0e+21

-2

2,5e+21

3,0e+21

0,0 0,0 0,2 0,4 0,6 0,8 1,0

Calculated Vzz (V.m )

Calculated Q

Very fine agreement between experimental and calculated values

M.Body, et al., J.Phys.Chem. A 2007, 111, 11873 (Univ. LeMans)

EFG (1021 V/m2) in YBa2Cu3O7

Site Y

theory exp. Ba theory exp. Cu(1) theory exp. Cu(2) theory exp. Cu(2) O(1) theory exp. O(2) theory exp. O(3) theory exp. O(4) theory exp.

Vxx -0.9 -8.7 8.4 -5.2 7.4 2.6 6.2 -5.7 6.1 12.3 10.5 -7.5 6.3 -4.7 4.0

Vyy 2.9 -1.0 0.3 6.6 7.5 2.4 6.2 17.9 17.3 -7.5 6.3 12.5 10.2 -7.1 7.6

Vzz -2.0 9.7 8.7 -1.5 0.1 -5.0 12.3 -12.2 12.1 -4.8 4.1 -5.0 3.9 11.8 11.6

0.4 0.8 0.9 0.6 1.0 0.0 0.0 0.4 0.3 0.2 0.2 0.2 0.2 0.2 0.3

standard LDA calculations give good EFGs for all sites except

K.Schwarz, C.Ambrosch-Draxl, P.Blaha, Phys.Rev. B42, 2051 (1990) D.J.Singh, K.Schwarz, K.Schwarz, Phys.Rev. B46, 5849 (1992)

Interpretation of O-EFGs in YBa2Cu3O7

px O(1) O(2) O(3) O(4) 1.18 py pz Vaa -6.1 Vbb Vcc 0.91 1.25 1.18 18.3 12.2 -4.8 O(2),O(3) 11.7 11.9 -4.9 -7.0 O(1) O(4)

1.01 1.21 1.21 1.18 1.19

11.8 -7.0 -7.0

1.00 1.18

0.99 -4.7

n p = p z ( p x + p y ) 2 EFG (p-contribution)

Asymmetry count 1

y x
EF Cu1-d O1-py partly occupied

1 p Vzz n p < 3 > p r

EFG is proportional to the asymmetric charge distribution around a given nucleus

difference density

Cu(2) and O(4) EFG as function of r

EFG is determined by the non-spherical charge density inside sphere (r )Y20 (r ) = LM (r )YLM Vzz dr = 20 (r ) / r dr 3 r LM

Cu(2)
r r

final EFG

O(4)

semicore and valence Cu-EFG contributions

semicore Cu 3p-states have very little importance valence 3d-states: large contribution due to smaller d-x2-y2 occupation valence 4p-states: large contribution of opposite sign. Originates from the tails of the O-2p orbitals (re-expanded as Cu 4p in the Cu atomic sphere, off-site contribution) usually only contributions within the first node or within 1 bohr are important.

general statements for EFG contributions Depending on the atom, the main EFG-contributions come from anisotropies in occupations of different orbitals or the radial wave functions of different orbitals)

semicore p-states: they are of course always fully occupied, but due to an anisotropic neighborhood they may slightly contract/expand in different directions. The effect depends on:

the energy and spatial localization: Ti 3p more important than Cu 3p (almost inert) the distance, type (atom) and geometry of the neighbors (a small octahedral distortion will produce a much smaller effect than a squareplanar coordination)

valence p-states : always important (on-site O 2p or offsite Cu 4p) valence d-states : in ionic or covalent TM compounds. In metals usually small.

LDA/GGA problems in correlated TM oxides

As shown before, the approximations for exchange-correlation (LDA, GGA) can have significant influence on the quality of the results for the class of compounds with so called correlated electrons. Such electrons are in particular TM-3d electrons in TM-oxides (or, more general, in most ionic TM-compounds), but also the 4f and 5f electrons of lanthanides or actinides. For these systems, beyond-GGA schemes like LDA+U or hybrid-functionals (mixing of Hartree-Fock+GGA) are necessary, as was demonstrated before for YBa2Fe2O5.

Another example of very bad EFGs within GGA would be the class of the undoped Cuprates (La2CuO4, YBa2Cu3O6), which are nonmagnetic metals instead of antiferromagnetic insulators in GGA. Both, doped and undoped cuprates have a planar Cu EFG in GGA-calculations, which is by a factor of 2-3 too small compared to experiments.

Cuprates: La2CuO4
LDA: nonmagnetic metal LDA+U: AFM insulator (in agreement with experiment)

lower Hubbard-band

upper HB

Magn. moments and EFG in La2CuO4

AMF
exp.

FLL

LDA+U gives AF insulator with reasonable momen U of 5-6 eV gives exp. EFG GGAs mimic a U of 1-2 eV

(EV-GGA more effective than PBE !!)

zz

YBa2Cu3O6
for LDA, AMF, FLL and DFT-double counting corrections. NM and AF refers to non-magnetic and antiferromagnetic solutions. U and J of 8 and 1 eV is applied to both Cu sites, except for LDA+U* where U is applied only to the Cu(2) site. Type Vzz -Cu(1) Vzz -Cu(2) LDA (NM) AMF-LDA+U (NM) AMF-LDA+U*(NM) AMF-LDA+U (AF) AMF-LDA+U*(AF) DFT-LDA+U(AF) FLL-LDA+U (AF) FLL-LDA+U*(AF) Experiment -8.1 -4.6 -8.0 -4.5 -8.0 -4.8 -8.3 -8.0 11.8 -3.7 -7.3 -7.2 -13.3 -13.3 -12.0 -12.3 -13.3 9.0
Cu(2) too small, Cu(1) ok Cu(2) still too small, Cu(1) wrong Cu(2) ok, Cu(1) wrong DFT similar to AMF Cu(2) ok,Cu(1) remains ok

Antiferromagn. FLL-calc. with U=6eV give again best results

p Vzz EFG analysis in YBa2Cu3O6:

1 r3

[ 12 ( p

+ p y ) pz

EFG contributions (for both spins and p-p and d-d contributions) in LSDA and LDA+U(DFT) Cu(1) Cu(2) NM-LDA AF-LDA+U(DFT) NM-LDA AF-LDA+U(DFT) large charge in z p-p (up) -12.2 -12.2 5.7 5.8 large negative EFG p-p (dn) -12.2 -12.2 5.7 6.3 d-d (up) 7.1 8.8 -7.4 5.5 d-d (dn) 7.1 8.8 -7.4 -31.1 large charge in xy Semicore 2.1 2.0 -0.1 1.7 large positive EFG Total -8.1 -4.8 -3.7 -12.0 Exp. 11.8 9.0 Partial charges and anisotropy counts n in LDA and antiferromagnetic LDA+U(DFT) Cu(1) Cu(2) NM-LDA AF-LDA+U(DFT) NM-LDA AF-LDA+U(DFT) 4pz 0.103 0.104 0.027 0.028 4px+py 0.041 0.042 0.131 0.140 np -0.083 -0.083 0.039 0.042 Cu(1) anisotropy increased in and AMF schems: wrong! dx2-y2 1.776 1.782 1.433 1.228 DFT Cu(2) has O in xy plane 2 dz 1.474 1.398 1.757 1.784 Cu(2) dx2-y2 depopulated: ok daver 1.802 1.818 1.815 1.841 nd 0.257 0.324 -0.294 -0.529 Cu(1) has O only in z

Summary

EFGs can routinely be calculated for all kinds of solids.

semi-core contribution large for left-atoms of the periodic table p-p contribution always large (on-site (eg. O-2p) vs. off-site (Fe-4p)) d-d (f-f) contributions for TM (lanthanide/actinide) compounds EFG stems from different orbital occupations due to covalency or crystal field effects forget point-charge models and Sternheimer anti-shielding factors correct structural data (internal atomic positions) correct theoretical description of the electronic structure

EFG is very sensitive to

highly correlated transition metal compounds (oxides, halides) 4f and 5f compounds beyond LDA (LDA+U, Hybrid-DFT, )

Literature

WIEN2k and APW-based methods:

P.Blaha, K.Schwarz, P.Sorantin and S.B.Trickey: Full-potential, linearized augmented plane wave programs for crystalline systems , Comp.Phys.Commun. 59, 399 (1990) P.Blaha and K.Schwarz: WIEN93: An energy band-structure program for ab initio calculations of electric field gradients in solids, NQI Newsletter Vol 1 (3), 32 (1994) K.Schwarz and P.Blaha: Description of an LAPW DF Program (WIEN95), in: Lecture notes in chemistry, Vol. 67, p.139, Ed. C.Pisani, Springer (Berlin 1996) H.Petrilli, P.E.Blchl, P.Blaha, and K.Schwarz: Electric-field-gradient calculations using the projector augmented wave method, Phys.Rev. B57, 14690 (1998) G.Madsen, P.Blaha, K.Schwarz, E.Sjstedt and L.Nordstrm: Efficient linearization of the augmented plane-wave method, Phys.Rev. B64, 195134 (2001) P.Blaha, K.Schwarz, G.Madsen, D.Kvasnicka and J.Luitz: WIEN2k: An augmented plane wave plus local orbitals program for calculating crystal properties. K.Schwarz, TU Wien, 2001 (ISBN 3-9501031-1-2) (http://www.wien2k.at) K.Schwarz, P.Blaha and G.K.H.Madsen: Electronic structure calculations of solids using the WIEN2k package for material sciences, Comp.Phys.Commun. 147, 71 (2002) D. J. Singh and L. Nordstrom: Planewaves, Pseudopotentials and the

Literature

DFT and beyond:

P. Hohenberg and W. Kohn: Inhomogeneous electron gas, Phys. Rev. 136, B864 1964. W. Kohn and L. J. Sham: Selfconistent equations including exchange and correlation effects, Phys. Rev. 140, A1133 1965. V. I. Anisimov, J. Zaanen, and O. K. Andersen: Band theory and Mott insulators: Hubbard U instead of Stoner I, Phys. Rev.B 44, 943 (1991). J. P. Perdew, K. Burke, and M. Ernzerhof: Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996); 78, 1396 (1997). A Primer in Density Functional Theory, edited by C. Fiolhais, F. Nogueira, and M. Marques, Springer, Berlin, 2003. F. Tran, P. Blaha, K. Schwarz, P. Novak: Hybrid exchange-correlation energy functionals for strongly correlated electrons: Applications to transition-metal monoxides; Phys.Rev B, 74 (2006), 155108. P. Haas, F. Tran, P. Blaha: Calculation of the lattice constant of solids with semilocal functionals; Physical Review B, 79 (2009), 085104, Physical Review B, 79 (2009), 209902(E) F.Tran and P.Blaha: Accurate band gaps of semiconductors and insulators with a semilocal exchange-correlation potential, Physical Review Letters, 102, (2009) 226401.

Literature

Hyperfine parameters using WIEN2k:

P.Blaha, K.Schwarz and P.Herzig: First-principles calculation of the electric field gradient of Li3N , Phys.Rev.Lett. 54, 1192 (1985) P.Blaha, K.Schwarz and P.H.Dederichs: First-principles calculation of the electric field gradient in hcp metals , Phys.Rev. B37, 2792 (1988) P.Blaha and K.Schwarz: Theoretical investigation of isomer shifts in Fe, FeAl, FeTi and FeCo , J.Phys.France C8, 101 (1988) P.Blaha, P.Sorantin, C.Ambrosch and K.Schwarz: Calculation of the electric field gradient tensor from energy band structures , Hyperfine Interactions 51, 917 (1989) P.Blaha and K.Schwarz: Electric field gradient in Cu2O from band structure calculations, Hyperfine Interact. 52, 153 (1989) P.Blaha: Calculation of the pressure dependence of the EFG in bct In, hcp Ti and Zn from energy band structures , Hyperfine Interact. 60, 773 (1990) C.Ambrosch-Draxl, P.Blaha and K.Schwarz: Calculation of EFGs in high Tc superconductors , Hyperfine Interactions 61, 1117 (1990) K.Schwarz, C.Ambrosch-Draxl, P.Blaha, Charge distribution and electricfield gradients in YBa2Cu3O7-x , Phys.Rev. B42, 2051 (1990) P.Blaha, K.Schwarz and A.K.Ray: Isomer shifts and electric field gradients in Y(Fe1xAlx)2, J.Magn.Mag.Mat. 104-107, 683 (1992) D.J.Singh, K.Schwarz, K.Schwarz: Electric-field gradients in YBa2Cu3O7: Discrepancy between experimental and local-density-approximation charge distributions,

Literature

P.Blaha, D.J.Singh, P.I.Sorantin and K.Schwarz: Electric field gradient calculations for systems with giant extended core state contributions, Phys.Rev. B46, 1321 (1992) W.Trger, T.Butz, P.Blaha and K.Schwarz: Nuclear quadrupole interaction of 199mHg in mercury(I) and mercury(II) halides, Hyperfine Interactions 80, 1109 (1993) P.Blaha, P.Dufek, and K.Schwarz: Electric field gradients, isomer shifts and hyperfine fields from band structure calculations in NiI2, Hyperfine Inter. 95, 257 (1995) P.Dufek, P.Blaha and K.Schwarz: Determination of the nuclear quadrupole moment of 57Fe, Phys.Rev.Lett. 75, 3545 (1995) P.Blaha, P.Dufek, K.Schwarz and H.Haas: Calculations of electric hyperfine interaction parameters in solids, Hyperfine Int. 97/98, 3 (1996) K.Schwarz, H.Ripplinger and P.Blaha: Electric field gradient calculations of various borides; Z.Naturforsch. 51a, 527 (1996) B.Winkler, P.Blaha and K.Schwarz: Ab initio calculation of electric-fieldgradient tensors of forsterite, American Mineralogist, 81, 545 (1996) H.Petrilli, P.E.Blchl, P.Blaha, and K.Schwarz: Electric-field-gradient calculations using the projector augmented wave method, Phys.Rev. B57, 14690 (1998) P.Blaha, K.Schwarz, W.Faber and J.Luitz: Calculations of electric field gradients in solids: How theory can complement experiment, Hyperfine Int. 126, 389 (2000)

Literature

G.Principi, T.Spataru, A.Maddalena, A.Palenzona, P.Manfrinetti, P.Blaha, K.Schwarz, V.Kuncser and G.Filotti: A Mssbauer study of the new phases Th4Fe13Sn5 and ThFe0.22Sn2, J.Alloys and Compounds 317-318, 567 (2001) R. Laskowski, G.K.H. Madsen, P. Blaha, K. Schwarz: Magnetic structure and electric-field gradients of uranium dioxide: An ab initio study ; Physical Review B, 69 (2004), S. 140408(R). P. Palade, G. Principi, T. Spataru, P. Blaha, K. Schwarz, V. Kuncser, S. Lo Russo, S. Dal Toe, V. Yartys: Mssbauer study of LaNiSn and NdNiSn compounds and their deuterides; Journal of Radioanalytical and Nuclear Chemistry, 266 (2005), 553 556. P. Blaha, K. Schwarz, P. Novak: Electric Field Gradients in Cuprates: Does LDA+U give the Correct Charge Distribution ?; International Journal of Quantum Chemistry, 101 (2005), 550 M. Body, C. Legein, J. Buzare, G. Silly, P. Blaha, C. Martineau, F. Calvayrac: Advances in Structural Analysis of Fluoroaluminates Using DFT Calculations of 27Al Electric Field Gradients; Journal of Physical Chemistry A, 111 (2007), S. 11873 11884. Seung-baek Ryu, Satyendra K. Das, Tilman Butz, Werner Schmitz, Christian Spiel, Peter Blaha, and Karlheinz Schwarz: Nuclear quadrupole interaction at 44Sc in the anatase and rutile modifications of TiO2 : Time-differential perturbed-angularcorrelation measurements and ab initio calculations, Physical Review B, 77 (2008), S. 094124