Hartree-Fock-SlaterMethod for Materials Science

Transcription

1 H. Adachi T. Mukoyama J. Kawai (Eds.) Hartree-Fock-SlaterMethod for Materials Science The DV-Xa Method for Design and Characterization of Materials With 132 Figures and 33 Tables 4u Sprin ger

2 Contents Part I Fundamental 1 DV-Xa Method and Molecular Structure H. Adachi Molecular Orbital Theory Discrete Variational (DV) Xa Molecular Orbital Method Molecular Orbital Calculation of H Covalency and Ionicity DV-Xa Molecular Orbital Calculation for CO Molecule 15 References 20 Part II Materials Science 2 Alloy Design Based on the DV-Xa Cluster Method M. Morinaga, Y. Murata, H. Yukawa Introduction DV-Xa Molecular Orbital Method Alloying Parameters d-orbital Energy Level, Md Bond Order, Bo Average Parameter Values for Typical Alloys Estimation of Alloy Properties Using Alloying Parameters Nickel Alloys 29 New PHACOMP Method 30 Alloying Vector 30 Target Region for Alloy Design 32 Alloy Modification Using the Bo-Md Diagram 32

3 X Contents High-Cr Ferritic Steels 33 Alloying Vector 33 ö Ferrite Formation 34 Evolution of Ferritic Steels Design of Structural Alloys Nickel-Based Single-Crystal Superalloys High-Cr Ferritic Steels Crystal Structure Maps for Intermetallic Compounds Hydrogen Storage Alloys Metal-hydrogen Interaction Roles of Hydride-Forming and Non-Forming Elements Criteria for Alloy Design 41 Alloy Cluster Suitable for Hydrogen Storage 41 Alloy Compositions 42 Mg-Based Alloys Proton-Conducting Perovskite-type Oxides Conclusion 46 References 46 3 Chemical Bonding Around Lattice Imperfections in 3d-Transition Metal Compounds M. Mizuno Introduction Computational Method Effect of Solute Atoms on the Chemical Bonding of FesC Crystal Structure and Cluster Models for Fe 3 C with Solute Atoms Pure Fe 3 C Fe 3 C with Solute Atoms Effect of Solute Atoms on Fe 3 C Effect of Solute Atoms in Other Transition Metal Carbides Chemical Bonding at the Fe/TiX (X = C, N, or O) Interfaces Model Clusters for the Fe/TiX Interfaces Bulk TiC, TiN, and TiO Preferred Position of Fe Atoms at the Fe/TiC Interface Analysis of the Chemical Bonding at the Fe/TiC, Fe/TiN, and Fe/TiO Interfaces Other Interfaces Conclusions 81 References 82 4 Ceramics T. Kamiya, N. Ohashi, J. Tanaka General Introduction 85

4 Contents XI 4.2 Characterization of Ceramics with the Assistance of DV-Xa Calculations Assignments for Electron Spectroscopy 88 Introduction 88 Calculation 91 Results 92 Remarks Prediction of Atomic Arrangements 93 Introduction Theory and Calculation Results 96 Remarks Assignments for the ESR Spectra Using Electron Density Calculations by DV-Xa 98 Introduction 98 Theory and Calculation Results Property and Structure Predictions for Ceramics Using DV-Xa Calculation of Structural and Dielectric Properties of Inorganic Crystals Using DV-Xa Basis Functions 103 Introduction 103 Calculation 104 Results Tight-binding Approach Using the DV-Xa Method 106 Introduction 106 Calculation Results Indirect Prediction of the Piezoelectric Property Change of Pb(Zr,Ti)0 3 Induced by the Addition of Impurities 112 Introduction 112 Calculation 113 Results Remarks 118 References Magnetic Properties K. Fukushima Introduction Computational Method and Models Results and Discussion Conclusions 127 References 127

5 XII Contents 6 Optical Materials K. Ogasawara, H. Adachi Introduction Optical Materials Based on Transition-Metal Ions Ligand-Field Theory First-principle Calculation of Multiplets DV-ME Method DV-ME Method Configuration Interaction CDC Approach Correlation Correction Transition Probability Calculation of the Absorption Spectrum of Ruby Model Cluster One-Electron Energy Level Multiplet Energy Level Absorption Spectra Calculation of the Absorption Spectrum of Co 2+ :ZnS Model Cluster One-Electron Energy Level Multiplet Energy Level Absorption Spectrum Summary 143 References Heavy Elements T. Ishii, M. Yamashita, R. Sekine, T. Enoki Introduction Method of Calculation Results and Discussion 150 References 159 Part III Spectroscopy 8 Radiative Transitions T. Mukoyama Introduction Transition Probability Dipole Matrix Element Molecular X-Ray Emission Test for X-Ray Emission Rates Validity of the DV Integration Method Electronic Relaxation Effect Contributions from Interatomic Transitions 177

6 Contents XIII 8.6 Chemical Effect of the Kß/Ka Ratios for 3d Elements Relation between Kß/Ka Ratios and the Number of 3d Electrons Summary 186 References Response to the Creation of a Core Hole in Transition-Metal Compounds J. Kawai Core-hole Spectroscopic Techniques Ionic Chemical Bond as a Perturbation of Atomic Structure Covalent Bond Formation Due to a Core Hole Charge Transfer Due to a Core Hole Calculation Details Cluster Size Difference Between ls _1 and laf -1 Hole States Difference Between ls" 1 and 2p~ l Hole States Effect of Bond Length Difference Charge-Transfer Effect Concluding Remarks 204 References Determining Electronic Structure from Auger Spectra in the Cluster Approximation L. Köver Introduction Effects of the Atomic Environment of Auger Spectra Excited from Solids X-ray Excited Auger Spectroscopy for Studying Chemical and Solid State Effects on Auger Spectra Local Charges in Binary Alloys Experimental Charge Transfer in CuPd Alloys Charge Transfer in A13Ni and AlNi 3 Alloys Generalized Electrostatic Model for Interpreting Auger Parameter Shifts and Final State Relaxation/Polarization Interpretation of K-Auger Satellite Structures in 3rf Metals and in Fluorides, Using the MO Cluster Approach KLL Auger Spectra of Metallic Cu and Ni: Calculation of the Satellite Main Line Energy Separation Using the DV-Xa Cluster Molecular Orbital Model F KLL Spectra in Fluorides: Determination of the Resonance Energy and Multiplet Structure Using DV-Xa Cluster Molecular Orbital Calculations Information on Local Electronic Structure and Correlation from Core-valence Auger Lineshapes 226

7 XIV Contents Local Electronic Structures in Phosphorus Oxyanions Core-valence AT-Auger Spectra of Metallic AI Local Electronic Structure in Al-Ni Alloys Summary 234 References 234 Index 237