Multiconfigurational Quantum Chemistry

1. Auflage 2016
ISBN: 978-0-470-63346-5
Verlag: Wiley

Buch, Englisch, 240 Seiten, Format (B × H): 161 mm x 244 mm, Gewicht: 496 g

The first book to aid in the understanding of multiconfigurational quantum chemistry, Multiconfigurational Quantum Chemistry demystifies a subject that has historically been considered difficult to learn. Accessible to any reader with a background in quantum mechanics and quantum chemistry, the book contains illustrative examples showing how these methods can be used in various areas of chemistry, such as chemical reactions in ground and excited states, transition metal and other heavy element systems. The authors detail the drawbacks and limitations of DFT and coupled-cluster based methods and offer alternative, wavefunction-based methods more suitable for smaller molecules.

Autoren/Hrsg.

Roos, Björn O

Lindh, Roland

Malmqvist

Malmqvist, Per ?ke

Veryazov, Valera

Widmark, Per-Olof

Fachgebiete

• Naturwissenschaften Physik Physik Allgemein Theoretische Physik, Mathematische Physik, Computerphysik
• Naturwissenschaften Chemie Chemie Allgemein Chemometrik, Chemoinformatik
• Naturwissenschaften Chemie Physikalische Chemie Quantenchemie, Theoretische Chemie

Inhaltsverzeichnis

Preface xi

Conventions and Units xiii

1 Introduction 1

1.1 References 4

2 Mathematical Background 7

2.1 Introduction 7

2.2 Convenient Matrix Algebra 7

2.3 Many-Electron Basis Functions 11

2.4 Probability Basics 14

2.5 Density Functions for Particles 16

2.6 Wave Functions and Density Functions 17

2.7 Density Matrices 18

2.8 References 22

3 Molecular Orbital Theory 23

3.1 Atomic Orbitals 24

3.1.1 The Hydrogen Atom 24

3.1.2 The Helium Atom 26

3.1.3 Many Electron Atoms 28

3.2 Molecular Orbitals 29

3.2.1 The Born–Oppenheimer Approximation 29

3.2.2 The LCAO Method 30

3.2.3 The Helium Dimer 34

3.2.4 The Lithium and Beryllium Dimers 35

3.2.5 The B to Ne Dimers 35

3.2.6 Heteronuclear Diatomic Molecules 37

3.2.7 Polyatomic Molecules 39

3.3 Further Reading 41

4 Hartree–Fock Theory 43

4.1 The Hartree–Fock Theory 44

4.1.1 Approximating the Wave Function 44

4.1.2 The Hartree–Fock Equations 45

4.2 Restrictions on The Hartree–Fock Wave Function 49

4.2.1 Spin Properties of Hartree–Fock Wave Functions 50

4.3 The Roothaan–Hall Equations 53

4.4 Practical Issues 55

4.4.1 Dissociation of Hydrogen Molecule 55

4.4.2 The Hartree-Fock Solution 56

4.5 Further Reading 57

4.6 References 58

5 Relativistic Effects 59

5.1 Relativistic Effects on Chemistry 59

5.2 Relativistic Quantum Chemistry 62

5.3 The Douglas–Kroll–Hess Transformation 64

5.4 Further Reading 66

5.5 References 66

6 Basis Sets 69

6.1 General Concepts 69

6.2 Slater Type Orbitals, STOs 70

6.3 Gaussian Type Orbitals, GTOs 71

6.3.1 Shell Structure Organization 71

6.3.2 Cartesian and Real Spherical Harmonics Angular Momentum Functions 72

6.4 Constructing Basis Sets 72

6.4.1 Obtaini

Über Autor(innen)

Björn O. Roos received his PhD inTheoretical Physics and is Professor Emeritus at Lund University. He is a former board member of the Swedish National Research Foundation, a member of the Swedish Royal Academy of Sciences, the Nobel Committee for Chemistry, the International Academy of Quantum Molecular Sciences, and is on the advisory editorial board for Chemical Physics Letter, Molecular Physics, International Journal of Quantum Chemistry, and Chemical Physics Physical Chemistry. Dr. Roos is the author of approximately 300 peer-reviewed articles in international journals, various book chapters, and is editor and co-author of text books for the European Summer School in Quantum Chemistry.