Relativistic Effects in Heavy-Element Chemistry and Physics

328 Pages·2003·9.35 MB·english

by  Bernd A. Hess (Ed.)

Relativistic Effects in Heavy-Element Chemistry and Physics
Wiley Series in Theoretical Chemistry
Series Editors
D. Clary, University College London, London, UK
A. Hinchliffe, UMIST, Manchester, UK
D. S. Urch, Queen Mary and Westfield College, London, UK
M. Springborg, Universitat des Saarlandes, Saarbrucken, Germany
Thermodynamics of Irreversible Processes: Applications to Diffusion and Rheology
Gerard D. C. Kuiken
Published 1994, ISBN 0 471 94844 6
Modelling Molecular Structures
Alan Hinchliffe
Published 1995, ISBN 0 471 95921 9 (cloth), ISBN 0 471 95923 5 (paper)
Published 1996, ISBN 0471 96491 3 (disk)
Molecular Interactions
Edited by Steve Scheiner
Published 1997, ISBN 0 471 97154 5
Density-Functional Methods in Chemistry and Materials Science
Edited by Michael Springborg
Published 1997, ISBN 0 471 96759 9
Theoretical Treatments of Hydrogen Bonding
DuSan Hadzi
Published 1997, ISBN 0 471 97395 5
The Liquid State - Applications of Molecular Simulations
David M. Heyes
Published 1997, ISBN 0 471 97716 0
Quantum-Chemical Methods in Main-Group Chemistry
Thomas M. Klapfitke and Axel Schulz
Published 1998, ISBN 0 471 97242 8
Electron Transfer in Chemistry and Biology: An Introduction to the Theory
Alexander M. Kuznetsov and Jens Ulstrup
Published 1998, ISBN 0 471 96749 1
Metal Clusters
Edited by Walter Ekardt
Published 1999, ISBN 0 471 98783 2
Methods of Electronic-Structure Calculations From Molecules to Solids
Michael Springborg
Published 2000, ISBN 0 471 97975 9 (cloth), 0 471 97976 7 (paper)
Modelling Molecular Structures, Second Edition
Alan Hinchliffe
Published 2000, ISBN 0 471 62380 6
Relativistic Effects in Heavy-Element
Chemistry and Physics
Edited by
Bernd A. Hess
Friedrich-Alexander-Universitat
Erlangen-Nurnberg, Germany
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library of Congress Cataloguing-in-Publication Data
Relativistic effects in heavy element chemistry and physics/edited by Bemd Hess.
p. cm. - (Wiley series in theoretical chemistry)
ISBN 0-470-84138-9 (cloth : alk. Paper)
1. Quantum chemistry. 2. Relativistic quantum theory. 3. Heavy elements. I. Hess, Bemd. II Series.
QD462.6.R2 R45 2002
541.2'8-dc21
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
ISBN 0470 84138 9
Produced from I&Tr^C files supplied by the authors, typeset by T&T Productions Ltd, London.
Printed and bound in in Great Britain by T J International Ltd, Padstow, Cornwall.
This book is printed on acid-free paper responsibly manufactured from sustainable forestry
in which at least two trees are planted for each one used for paper production.
SERIES PREFACE
Theoretical chemistry is one of the most rapidly advancing and exciting fields in the
natural sciences today. This series is designed to show how the results of theoretical
chemistry permeate and enlighten the whole of chemistry together with the multi-
farious applications of chemistry in modern technology. This is a series designed for
those who are engaged in practical research. It will provide the foundation for all
subjects which have their roots in the field of theoretical chemistry.
How does the materials scientist interpret the properties of the novel doped fullerene
superconductor or a solid-state semiconductor? How do we model a peptide and
understand how it docks? How does an astrophysicist explain the components of
the interstellar medium? Where does the industrial chemist turn when he wants to
understand the catalytic properties of a zeolite or a surface layer? What is the meaning
of 'far-from-equilibrium' and what is its significance in chemistry and in natural
systems? How can we design the reaction pathway leading to the synthesis of a
pharmaceutical compound? How does our modelling of intermolecular forces and
potential energy surfaces yield a powerful understanding of natural systems at the
molecular and ionic level? All these questions will be answered within our series
which covers the broad range of endeavour referred to as 'theoretical chemistry'.
The aim of the series is to present the latest fundamental material for research
chemists, lecturers and students across the breadth of the subject, reaching into the
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It will emphasize the transfer of theoretical ideas and results to practical situations
so as to demonstrate the role of theory in the solution of chemical problems in the
laboratory and in industry.
D. CLARY, A. HINCHLIFFE, D. S. URCH AND M. SPRINGBORG
JUNE 1994
List of Contributors xi
Foreword xiii
Preface xvii
1 Basic Theory and Quantum Electrodynamics in
Strong Fields 1
1.1 Introduction 1
1.2 Electrons in Superintense Laser Fields 4
1.2.1 Model simulations 6
1.2.2 Laser—electron interaction from
classical electrodynamics 10
1.3 Electron-Positron Pair Creation in Relativistic
Heavy-Ion Collisions 15
1.3.1 Theoretical framework 16
1.3.2 Coupled-channel calculations 18
1.3.3 Finite-element method 20
1.3.4 Electromagnetic pair production:
the ultrarelativistic limit 23
1.4 Relativistic and QED Effects in Highly Charged Ions 28
1.4.1 Relativistic description of few-electron systems 32
1.4.2 Relativistic model Hamiltonians for
many-electron systems 36
1.4.3 Bound-state QED 39
1.4.4 Self-energy correction 43
1.4.5 Vacuum polarization 45
1.4.6 Lamb-shift calculations for highly charged ions 47
1.4.7 Hyperfine structure and bound-electron g-factor 54
viii CONTENTS
2 Four-Component Ab Initio Methods for Atoms,
Molecules and Solids 61
2.1 Introduction 61
2.2 General Many-Electron Formalism 63
2.3 Atomic-Structure Calculations 67
2.3.1 Methods and programs 68
2.3.2 Term values 71
2.3.3 Transition probabilities and lifetimes 71
2.3.4 Hyperfine structure 73
2.3.5 Photoionization and electron-atom scattering 73
2.4 Molecular Structure Calculations 74
2.4.1 Molecular one-electron functions 74
2.4.2 Program development 76
2.4.3 Avoiding (SS | SS) integrals 79
2.4.4 The nonrelativistic limit within the basis set approach 80
2.4.5 Electronic structure calculations 80
2.4.6 Lanthanide and actinide contraction 84
2.4.7 Phosphorescence 85
2.4.8 Parity violation 85
2.4.9 Calculation of properties from response theory 86
2.5 Electronic Structure of Solids 87
2.6 Concluding Remarks and Perspective 88
3 Relativistic Quantum Chemistry with Pseudopotentials
and Transformed Hamiltonians 89
3.1 Introduction 89
3.2 Transformed Hamiltonians: Theory 91
3.2.1 Two-component all-electron methods for
spin-orbit coupling 98
3.3 Transformed Hamiltonians: Applications 101
3.3.1 Small molecules 101
3.3.2 Metal clusters and metal complexes 103
3.3.3 Properties depending on spin—orbit coupling 104
3.4 Valence-Only Effective Hamiltonians 106
3.4.1 Model potentials 108
3.4.2 Pseudopotentials 111
3.4.3 Shape-consistent pseudopotentials 112
3.4.4 Energy-consistent pseudopotentials 113
3.4.5 Core—core/nucleus repulsion correction 115
3.4.6 Core polarization potentials 115
3.4.7 Choice of the core 116
3.5 Effective Core Potentials: Applications 117
CONTENTS ix
4 Relativistic Density Functional Theory
4.1 Introduction
4.2 Foundations
4.2.1 Existence theorem
4.2.2 Single-particle equations
4.3 Implicit Density Functionals
4.3.1 Optimized potential method
4.3.2 Results for the exact exchange
4.3.3 Correlation
4.4 Explicit Density Functionals
4.4.1 Local density approximation
4.4.2 Generalized gradient approximation
4.5 Norm-Conserving Pseudopotentials
4.5.1 Relativistic Troullier—Martins scheme
4.5.2 Results for the exact exchange
4.6 Applications of RDFT using the Relativistic
Discrete Variational Method 152
4.6.1 Results 154
4.6.2 Geometry optimization 155
4.6.3 Adsorption on surfaces 158
4.6.4 Improved numerical integration scheme 159
5 Magnetic Phenomena in Solids 163
5.1 Introduction 163
5.2 Formalism 165
5.2.1 Relativistic density functional theory 165
5.2.2 Relativistic Bogoliubov—de Gennes equations 169
5.2.3 Multiple scattering formalism 175
5.3 Applications 180
5.3.1 Ground-state properties 180
5.3.2 Surfaces 187
5.3.3 Noncollinear spin structures 191
5.3.4 Linear response 196
5.3.5 Spectroscopy 206
6 Experimental and Theoretical Study of the Chemistry of
the Heaviest Elements 219
6.1 Introduction 219
6.2 Theory 220
6.3 Experiment 224
6.3.1 Target and transport systems 224
x CONTENTS
6.4 Element 105 227
6.4.1 Theoretical predictions of complex formation of
element 105 in aqueous acidic solutions 227
6.4.2 Experimental results 230
6.5 Element 106 234
6.5.1 Theoretical predictions 234
6.5.2 Experimental results 240
6.6 Summary 243
7 Experimental Probes for Relativistic Effects in the
Chemistry of Heavy d and f Elements 245
7.1 Introduction 245
7.2 Gas-Phase Ion Chemistry of Heavy Elements 245
7.2.1 Thermochemistry 246
7.2.2 Coordination chemistry 248
7.2.3 Reactivity 251
7.3 Structural Chemistry of Gold Compounds in
the Condensed Phase 254
7.3.1 AuL+: a big proton? 254
7.3.2 Aurophilicity 255
7.3.3 Ligand design 256
7.4 Conclusions 257
Appendix A 259
References 261
Index 301