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Solid state calculations using WIEN2k

Karlheinz Schwarz

*

, Peter Blaha

Institute for Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/165-TC, A-1060 Vienna, Austria

Abstract

To study solid materials on the atomic scale one often starts with an ideal crystal at zero temperature and calculatesits electronic structure by means of density functional theory (DFT). This allows a quantum mechanical treatment of the physics that underlines properties such as relative stability, chemical bonding, relaxation of the atoms, phasetransitions, electrical, mechanical, optical or magnetic behavior, etc. For the solution of the DFT equations severalmethods have been developed. The linearized-augmented-plane-wave method is one of the most accurate methods. It isembodied in the computer code––WIEN2k––which is now used worldwide by more than 500 groups to solve crystalproperties on the atomic scale (seewww.wien2k.at). Nowadays calculations of this type can be done––on suﬃcientlypowerful computers––for systems containing about 100 atoms per unit cell. Chromium dioxide CrO

2

is selected as arepresentative example using both, bulk and surface structures. References to other applications are given.

Ó

2003 Elsevier B.V. All rights reserved.

PACS:

71.10; 71.15; 71.20; 71.22

Keywords:

WIEN2k; Density functional theory (DFT); Electronic structure

1. Introduction

In advanced solid materials, which are of greattechnological interest, several parameters such astemperature, pressure, structure, composition, anddisorder determine their properties. They aregoverned by very diﬀerent length and time scaleswhich may vary by many orders of magnitudedepending on their applications. Let us focus onthe length scale, where from meters (m) down tomicrometers (

l

m) classical mechanics and contin-uum models are the dominating concepts to in-vestigate the properties of the correspondingmaterials. However, when one comes to the nano-meter (nm) scale or atomic dimensions measuredin

AA, the properties are determined by the elec-tronic structure of the solid.In the development of modern materials anunderstanding on the atomic scale is frequentlyessential in order to replace trial and error proce-dures by a systematic materials design. Moderndevices in the electronic industry provide such anexample, where the increased miniaturization isone of the key advances. Other applications arefound in the area of magnetic recording or otherstorage media. In chemistry heterogeneous catal-ysis is a typical example, in which one likes tounderstand the details of catalytic processes be-tween molecules interacting with a solid surface asfor example in a zeolite.

Computational Materials Science 28 (2003) 259–273www.elsevier.com/locate/commatsci

*

Corresponding author.

E-mail address:

URL:

http://info.tuwien.ac.at/theochem/.0927-0256/$ - see front matter

Ó

2003 Elsevier B.V. All rights reserved.doi:10.1016/S0927-0256(03)00112-5

One possibility to study complex systems is toperform computer simulations. Calculation of solids in general (metals, insulators, semiconduc-tors, minerals, etc.) can be performed with a va-riety of methods from classical to quantummechanical approaches. The former are force ﬁeldschemes, in which the forces that determine theinteractions between the atoms are parameterizedin order to reproduce a series of experimental datasuch as equilibrium geometries, bulk moduli orspecial vibrational frequencies (phonons). Theseschemes have reached a high level of sophisticationand are often used within a given class of materialsprovided good parameters are already knownfrom closely related systems. If, however, suchparameters are not available, or if a system showsunusual phenomena that are not yet understood,one often must rely on ab initio calculations. Theseare more demanding in terms of computer re-quirements and thus allow only the treatment of smaller unit cells than force-ﬁeld calculations. Theadvantage of ﬁrst-principle (ab initio) methods liesin the fact that they can be carried out withoutany experimental knowledge of the system. In thefollowing we will restrict ourselves to ab initiomethods and sketch their main characteristics.The fact that electrons are indistinguishable andare Fermions requires that their wave functionsmust be anti-symmetric when two electrons areinterchanged. This situation leads to the phe-nomenon of exchange. There are two types of approaches for a full quantum mechanical treat-ment, HF and DFT. The traditional scheme is (orwas) the Hartree Fock (HF) method which isbased on a wave function description (with oneSlater determinant). Exchange is treated exactlybut correlation eﬀects are ignored by deﬁnition.The latter can be included by more sophisticatedapproaches such as the conﬁguration interactionscheme that progressively requires more computertime with a scaling as bad as

N

7

when the systemsize (

N

) grows. As a consequence it is only feasibleto study small systems, which contain a few atoms.An alternative scheme is density functionaltheory (DFT) that is commonly used to calculatethe electronic structure of complex systems con-taining many atoms such as large molecules orsolids. It is based on the electron density ratherthan on wave functions and treats exchange andcorrelation, but both approximately. It will bediscussed in the next section.The ideal crystal is deﬁned by the unit cellwhich may contain several (up to about 100)atoms. Periodic boundary conditions are used todescribe the inﬁnite crystal by knowing the prop-erties in one unit cell. Translational and pointgroup symmetry operations (inversion, rotation,mirror planes, etc.) that leave the ideal crystal in-variant allow to simplify the calculations, which allcorrespond to the absolute temperature zero(

T

¼

0).

2. Density functional theory

2.1. The Kohn–Sham equation

The well-established scheme to calculate elec-tronic properties of solids is based on DFT, forwhich Walter Kohn has received the Nobel Prizein chemistry in 1998. DFT is a universal approachto the quantum mechanical many-body problem,where the system of interacting electrons is map-ped in a unique manner onto an eﬀective non-interacting system with the same total density.Hohenberg and Kohn [1] have shown that theelectron density

.

uniquely deﬁnes the total energy

E

tot

of a system and is a functional

E

tot

ð

q

Þ

of thedensity:

E

tot

ð

q

Þ ¼

T

s

ð

q

Þ þ

E

ee

ð

q

Þ þ

E

Ne

ð

q

Þ þ

E

xc

ð

q

Þ þ

E

NN

:

ð

1

Þ

The diﬀerent electronic contributions are conven-tionally labeled as, respectively, the kinetic energy(of the non-interacting particles), the electron– electron repulsion, nuclear–electron attraction,and exchange-correlation energies. The last termcorresponds to the repulsive Coulomb energy of the ﬁxed nuclei

E

NN

.The most eﬃcient way to minimize

E

tot

bymeans of the variational principle is to introduceorbitals

v

ik

constrained to construct the densitiesas a sum over occupied orbitals according to theaufbau principle (with increasing energy)

q

ð

r

Þ ¼

X

i

;

k

q

ik

j

v

ik

ð

r

Þj

2

:

ð

2

Þ

260

K. Schwarz, P. Blaha / Computational Materials Science 28 (2003) 259–273

Here, the

q

ik

are occupation numbers such that0

6

q

ik

6

1

=

w

k

, where

w

k

is the symmetry-requiredweight of point

k

. Then variation of

E

tot

gives a setof eﬀective one-particle Schr

€

oodinger equations(written for an atom in Rydberg atomic units), theso-called Kohn–Sham equations [2],

½Àr

2

þ

V

Ne

þ

V

ee

þ

V

xc

v

ik

ð

r

Þ ¼

ik

v

ik

ð

r

Þ

;

ð

3

Þ

which must be solved. The non-interacting parti-cles of this auxiliary system move in an eﬀectivelocal one-particle potential, which consists of aclassical mean-ﬁeld (Hartree) part and an ex-change-correlation part

V

xc

(due to quantum me-chanics) that, in principle, incorporates allcorrelation eﬀects exactly. The KS equations mustbe solved in an iterative process till self-consistencyis reached, since ﬁnding the KS orbitals requiresthe knowledge of the potentials which themselvesdepend on the density and thus on the orbitalsagain.The exact functional form of

E

xc

or the poten-tial

V

xc

is not known and thus one needs to makeapproximations. Early applications were done byusing results from quantum Monte Carlo calcula-tions for the homogeneous electron gas, for whichthe problem of exchange and correlation can besolved numerically with high accuracy, leading tothe original local density approximation (LDA).LDA works reasonably well but has some short-comings mostly due to the tendency of overbind-ing, which cause e.g. too small lattice constants.Modern versions of DFT, especially those usingthe generalized gradient approximation (GGA),improve the LDA by adding gradient terms of theelectron density and reach (almost) chemical ac-curacy. At present the version by Perdew–Burke– Ernzerhof is the recommended option for solids[3].In the study of large systems the strategy of schemes based on HF or DFT diﬀer. In HF basedmethods the Hamiltonian is well deﬁned but canbe solved only approximately. In DFT, however,one must ﬁrst choose (approximate) the functionalthat is used to represent the exchange and corre-lation eﬀects but then this eﬀective Hamiltoniancan be solved almost exactly, i.e. with very highnumerical accuracy. Thus the approximation nec-essarily enters in both cases but the sequence isreversed. This perspective illustrates the impor-tance of improving the functional in DFT calcu-lations, since this deﬁnes the quality of thecalculation.

2.2. Spin polarization and magnetism

Magnetism can come from localized electrons(e.g. from the 4f electron in rare earth elements) orfrom delocalized electrons. In the latter case theitinerant electrons can be well described by bandtheory. Without spin–orbit coupling the magne-tism originates from the spin polarization, whereasthe orbital moment is often quenched. For exam-ple, Fe, Co, Ni are ferromagnets (FM) which fallin this category. In this case DFT is generalized toallow for a spin polarization, in which the spin-upand spin-down electrons move in spin-dependentpotentials, which can be deduced from the corre-sponding spin densities, for example using thelocal spin density approximation. Another case areantiferromagnets (AFM) (e.g. bcc Cr) in whichneighboring atoms have the opposite spin align-ment but the magnitude of the moment at each siteis the same. The net bulk magnetization vanishesfor AFM. When the magnitude diﬀers we haveferrimagnetism and a net magnetization. All thesecases belong to collinear magnets. The orientationof the magnetic moment with respect to the crystalaxis is only deﬁned when spin–orbit coupling isincluded. There are more complicated magneticstructures such as canted magnetic moments orspin spirals. In such cases the direction of themagnetization varies with position and this iscalled non-collinear magnetism.

2.3. Choice of basis set, wave function, and potential

Many methods are available to solve the DFTequations. Essentially all use a linear combinationof basis functions. Some use a linear combinationof atomic orbitals (LCAO) method with Gauss-ian or Slater type orbitals (GTOs or STOs) othersuse muﬃn tin orbitals (MTOs) as in linear com-bination of MTOs or augmented spherical wave.In the former cases the basis functions are given inanalytic form, but in the latter the radial wavefunctions are obtained by numerically integrating

K. Schwarz, P. Blaha / Computational Materials Science 28 (2003) 259–273

261