Electronic Structure Methods for Complex Materials

Transcription

1 Electronic Structure Methods for Complex Materials The orthogonalized linear combination of atomic orbitals WAI-YIM CHING and PAUL RULIS University of Missouri-Kansas City, USA OXFORD UNIVERSITY PRESS

2 1 Electronic Structure Methods in Materials Theory 1.1 Introduction One electron methods Quantum chemical approaches and solid state methods The OLCAO method 3 2 Historical Account of the LCAO Method Early days of the band theory of solids Origin of the LCAO method Use of Gaussian orbitals in LCAO calculations Beginning of the OLCAO method Current status and future trends of the OLCAO method 11 3 Basic Theory and Techniques of the OLCAO Method The atomic basis functions Bloch functions and the Kohn-Sham equation The site-decomposed potential function The technique of Gaussian transformation The technique of core orthogonalization Brillouin zone integration Special advantages in the OLCAO method 32 4 Calculation of Physical Properties Using the OLCAO Method Band structure and band gap Density of states and its partial components Effective charges, bond order, and the localization index Spin-polarized band structures Scalar relativistic corrections and spin-orbit coupling Magnetic properties Linear optical properties and dielectric functions Conductivity function in metals Non-linear optical properties of insulators Bulk properties and geometry optimization 50 i

3 5 Application to Semiconductors and Insulators 5.1 Elemental and binary semiconductors 5.2 Binary insulators 5.3 Oxides Binary oxides Ternary oxides Laser host crystals Quaternary oxides and other complex oxides 5.4 Nitrides Binary nitrides Spinel nitrides Ternary and quaternary nitrides and oxynitrides Other complex nitrides 5.5 Carbides SiC Other carbides 5.6 Boron and boron compounds Elemental boron B 4 C Other boron compounds Other forms of complex boron compounds 5.7 Phosphates Simple phosphates: AIPO Complex phosphates: KTP Lithium iron phosphate: LiFeP04 6 Application to Crystalline Metals and Alloys 6.1 Elemental metals and alloys Elemental metals Fe borides Fe nitrides Yttrium iron garnet 6.2 Permanent hard magnets Application to R^Fe^B crystals Further applications to Nd2Fej4B Application to Re2Fe 7 and related phases 6.3 High T c superconductors YBCO superconductor Other oxide superconductors Non-oxide superconductors 6.4 Other recent studies on metals and alloys Mo-Si-B alloys MAX phases 7 Application to Complex Crystals 7.1 Carbon-related systems Bucky-ball (Cgo) and alkali-doped C60 crystals Negative curvature graphitic carbon structures

4 Graphene, graphite, and carbon nanotubes Graphene and graphite Carbon nanotubes Polymeric crystals Organic crystals Organic superconductors Fe-TCNE Herapathite crystal Bioceramic crystals Calcium apatite crystals a- and ß-tricalcium phosphate 8 Application to Non-Crystalline Solids a Liquids 8.1 Amorphous Si and a-siü Amorphous Si and hydrogenated a-si Amorphous SiC>2 and a-sio x glasses Other glassy systems 8.2 Metallic glasses Cu x Zri_ x metallic glass Other metallic glasses Transport properties in metallic glasses Recent efforts on metallic glasses 8.3 Intergranular glassy films The basal model The prismatic model Prismatic-basal model (Yoshiya model) 8.4 Model of bulk water 8.5 Models for molten salts: NaCl and KCl 8.6 Models for concrete 9 Application to Impurities, Defects, and Surfaces 9.1 Isolated vacancies and substitutional impurities Isolated vacancies Single impurities or dopants 9.2 Vacancies and impurities in MgAl2Ü4 (spinel) Strategy Effect of inversion Effect of isolated vacancies Effect of Fe substitution 9.3 Impurity vacancy complexes 9.4 Grain boundary models Grain boundaries in 1X-AI2O Passive defects Grain boundary in SrTi Surfaces 9.6 Interfaces

5 10 Application to Biomolecular Systems 10.1 Vitamin B12 cobalamins 10.2 b-dna modeis 10.3 Collagen modeis 10.4 Other biomolecular systems 11 Application to Core Level Spectroscopy 11.1 Basic principles of the supercell OLCAO method 11.2 Select examples Simple crystals Complex crystals Y-K edge in different local environments Boron and boron-rich compounds Substitutional defects in crystals Biomolecular systems Application to grain boundaries and surfaces Application to intergranular glassy films Statistical description of O-K edges in bulk water 11.3 Spectral imaging Introduction Procedures for SI Application to a Si defect model 11.4 Further development of the supercell OLCAO method 12 Enhancement and Extension of the OLCAO Method 12.1 Versatility The OLCAO basis set The OLCAO potential and charge density representation Relativistic OLCAO Exchange-correlation functionals Magnetism and non-collinear spin polarization Configuration interaction Hamaker constants and long-range van der Waals-London interaction 12.2 Efficiency The memory hierarchy Modularization Parallelization 12.3 Ease of use User interface and control Interaction with third party software Data visualization Appendices A. Database for Atomic Basis Functions B. Database for Initial Atomic Potential Functions

6 XIII C. Current Implementation of the OLCAO Suite 270 C.l Introduction 270 C.2 Input generation 271 C.3 Program execution 282 C.4 Results analysis 295 D. Examples of Computational Statistics 297 Index 301