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Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science, 2nd Edition

Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science, 2nd Edition

Markus Reiher, Alexander Wolf

ISBN: 978-3-527-66758-1 September 2014 750 Pages

 E-Book

$177.99

Description

Einstein proposed his theory of special relativity in 1905. For a long time it was believed that this theory has no significant impact on chemistry. This view changed in the 1970s when it was realized that (nonrelativistic) Schrödinger quantum mechanics yields results on molecular properties that depart significantly from experimental results. Especially when heavy elements are involved, these quantitative deviations can be so large that qualitative chemical reasoning and understanding is affected. For this to grasp the appropriate many-electron theory has rapidly evolved. Nowadays relativistic approaches are routinely implemented and applied in standard quantum chemical software packages. As it is essential for chemists and physicists to understand relativistic effects in molecules, the first edition of "Relativistic Quantum Chemistry - The fundamental Theory of Molecular Science" had set out to provide a concise, comprehensive, and complete presentation of this theory.

This second edition expands on some of the latest developments in this fascinating field. The text retains its clear and consistent style, allowing for a readily accessible overview of the complex topic. It is also self-contained, building on the fundamental equations and providing the mathematical background necessary. While some parts of the text have been restructured for the sake of clarity a significant amount of new content has also been added. This includes, for example, an in-depth discussion of the Brown-Ravenhall disease, of spin in current-density functional theory, and of exact two-component methods and its local variants.
A strength of the first edition of this textbook was its list of almost 1000 references to the original research literature, which has made it a valuable reference also for experts in the field. In the second edition, more than 100 additional key references have been added - most of them considering the recent developments in the field.
Thus, the book is a must-have for everyone entering the field, as well as for experienced researchers searching for a consistent review.
Preface

INTRODUCTION
Philosophy of this Book
Short Reader's Guide
Notational Conventions and Choice of Units

PART I: Fundamentals

ELEMENTS OF CLASSICAL MECHANICS AND ELECTRODYNAMICS
Elementary Newtonian Mechanics
Lagrangian Formulation
Hamiltonian Mechanics
Elementary Electrodynamics

CONCEPTS OF SPECIAL RELATIVITY
Einstein's Relativity Principle and Lorentz Transformations
Kinematic Effects in Special Relativity
Relativistic Dynamics
Covariant Electrodynamics
Interaction of Two Moving Charged Particles

BASICS OF QUANTUM MECHANICS
The Quantum Mechanical State
The Equation of Motion
Observables
Angular Momentum and Rotations
Pauli Antisymmetry Principle

PART II: Dirac's Theory of the Electron

RELATIVISTIC THEORY OF THE ELECTRON
Correspondence Principle and Klein-Gordon Equation
Derivation of the Dirac Equation for a Freely Moving Electron
Solution of the Free-Electron Dirac Equation
Dirac Electron in External Electromagnetic Potentials
Interpretation of Negative-Energy States: Dirac's Hole Theory

THE DIRAC HYDROGEN ATOM
Separation of Electronic Motion in a Nuclear Central Field
Schrödinger Hydrogen Atom
Total Angular Momentum
Separation of Angular Coordinates in the Dirac Hamiltonian
Radical Dirac Equation for Hydrogen-Like Atoms
The Nonrelativistic Limit
Choice of the Energy Reference and Matching Energy Scales
Wave Functions and Energy Eigenvalues in the Coulomb Potential
Finite Nuclear Size Effects
Momentum Space Representation

PART III: Four-Component Many-Electron Theory

QUANTUM ELECTRODYNAMICS
Elementary Quantities and Notation
Classical Hamiltonian Description
Second-Quantized Field-Theoretical Formulation
Implications for the Description of Atoms and Molecules

FIRST-QUANTIZED DIRAC-BASED MANY-ELECTRON THEORY
Two-Electron Systems and the Breit Equation
Quasi-Relativistic Many-Particle Hamiltonians
Born-Oppenheimer Approximation
Tensor Structure of the Many-Electron Hamiltonian and Wave Function
Approximations to the Many-Electron Wave Function
Second Quantization for the Many-Electron Hamiltonian
Derivation of Effective One-Particle Equations
Relativistic Density Functional Theory
Completion: The Coupled-Cluster Expansion

MANY-ELECTRON ATOMS
Transformation of the Many-Electron Hamiltonian to Polar Coordinates
Atomic Many-Electron Wave Function and jj-Coupling
One- and Two-Electron Integrals in Spherical Symmetry
Total Expectation Values
General Self-Consistent-Field Equations and Atomic Spinors
Analysis of Radial Functions and Potentials at Short and Long Distances
Numerical Discretization and Solution Techniques
Results for Total Energies and Radial Functions

GENERAL MOLECULES AND MOLECULAR AGGREGATES
Basis Set Expansion of Molecular Spinors
Dirac-Hartree-Fock Electronic Energy in Basis Set Representation
Molecular One- and Two-Electron Integrals
Dirac-Hartree-Fock-Roothaan Matrix Equations
Analytic Gradients
Post-Hartree-Fock Methods

PART IV: Two-Component Hamiltonians

DECOUPLING THE NEGATIVE-ENERGY STATES
Relations of Large and Small Components in One-Electron Equations
Closed-Form Unitary Transformations of the Dirac Hamiltonian
The Free-Particle Foldy-Wouthuysen Transformation
General Parametrization of Unitary Transformation
Fold-Wouthuysen Expansion in Powers of 1/c
The Infinite-Order Two-Component Two-Step Protocol
Toward Well-Defined Analytic Block-Diagonal Hamiltonians

DOUGLAS-KROLL-HESS THEORY
Sequential Unitary Decoupling Transformations
Explicit Form of the DKH Hamiltonians
Infinite-Order DKH Hamiltonians and the Arbitrary-Order DKH Method
Many-Electron DKH Hamiltonians
Computational Aspects of DKH Calculations

ELIMINATION TECHNIQUES
Naive Reduction: Pauli Elimination
Breit-Pauli Theory
The Cowan-Griffin and Wood-Boring Approaches
Elimination for Different Representations of Dirac Matrices
Regular Approximations

PART V: Chemistry with Relativistic Hamiltonians

SPECIAL COMPUTATIONAL TECHNIQUES
From the Modified Dirac Equation to Exact-Two-Component Methods
Locality of Relativistic Contributions
Local Exact Decoupling
Efficient Calculation of Spin-Orbit Coupling Effects
Relativistic Effective Core Potentials

EXTERNAL ELECTROMAGNETIC FIELDS AND MOLECULAR PROPERTIES
Four-Component Perturbation and Response Theory
Reduction to Two-Component Form and Picture Change Artifacts
Douglas-Kroll-Hess Property Transformations
Magnetic Fields in Resonance Spectroscopies
Electric Field Gradient and Nuclear Quadrupole Moment
Parity Violation and Electro-Weak Chemistry

RELATIVISTIC EFFECTS IN CHEMISTRY
Effects in Atoms with Consequences for Chemical Bonding
Is Spin a Relativistic Effect?
Z-Dependence of Relativistic Effects: Perturbation Theory
Potential Energy Surfaces and Spectroscopic Parameters
Lanthanides and Actinides
Electron Density of Transition Metal Complexes
Relativistic Quantum Chemical Calculations in Practice

APPENDIX
Vector and Tensor Calculus
Kinetic Energy in Generalized Coordinates
Technical Proofs for Special Relativity
Relations for Pauli and Dirac Matrices
Fourier Transformations
Gordon Decomposition
Discretization and Quadrature Schemes
List of Abbreviations and Acronyms
List of Symbols
Units and Dimensions

The new edition is updated to include the latest developments in the field. Some content of the chapters has been restructured for the sake of clarity.

A significant amount of completely new content including:

- extension of the discussion of continuum dissolution

- extended discussion of spin in relativistic density functional theory

- exact-decoupling procedures with a focus on X2C

- local approximations to exact-decoupling methods

- more than 100 new key references