Table Of ContentTHEORETICAL CHEMISTRY AND PHYSICS OF HEAVY
AND SUPERHEAVY ELEMENTS
Progress in Theoretical Chemistry and Physics
VOLUME 11
Honorary Editor:
w'N. Lipscomb (Harvard University, Cambridge, MA, U.S.A.)
Editors-in-Chiej'
J. Maruani (Laboratoire de Chimie Physique, Paris, France)
S. Wilson (Rutherford Appleton Laboratory, Oxfordshire, u.K.)
Editorial Board:
H. Ägren (Royal Institute ofTechnology, Stockholm, Sweden)
D. Avnir (Hebrew University of Jerusalem, Israel)
J. Cioslowski (Florida State University, Tallahassee, FL, U.S.A.)
R. Daudel (EuropeanAcademy ofSciences, Arts and Humanities, Paris, France)
G. Delgado-Barrio (Instituto de Matematicas y Fisica Fundamental, Madrid, Spain)
E.K.U. Grass (Freie Universität, Berlin, Germany)
W.F. van Gunsteren (ETH-Zentrum, Zürich, Switzerland)
K. Hirao (University ofTokyo, Japan)
I. Hubac (Komensky University, Bratislava, Slovakia)
M.P. Levy (Tulane University, New Orleans, LA, U.S.A.)
R. McWeeny (Universita di Pisa, Italy)
P.G. Mezey (University of Saskatchewan, Saskatoon, SK, Canada)
M.A.C. Nascimento (Instituto de Quimica, Rio de Janeiro, Brazil)
N. Rahman (Dipartimento di Scienze Chimiche, Trieste, Italy)
S.D. Schwartz (Yeshiva University, Bronx, NY, U.S.A.)
S. Suhai (Cancer Research Center, Heidelberg, Germany)
O. Tapia (University of Uppsala, Sweden)
P.R. Taylor (University ofWarwick, Coventry, U.K.)
R.G. Woolley (Nottingham Trent University, Nottingham, u.K.)
Former Editors and Editorial Board Members:
I. Prigogine (deceased)
1. Rychlewski (deceased)
Y.G. Smeyers (deceased)
G.L. Malli (resigned)
The titles published in this series are listed at the end al this valurne.
Theoretical Chemistry and
Physics of Heavy
and Superheavy Elements
Edited by
U. Kaldor
School of Chemistry,
Tel Aviv University, Tel Aviv, Israel
and
S. Wilson
Rutherford Appleton Laboratory,
Chi/ton, Oxfordshire, England
Springer-Science+Business Media, B.V.
A c.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-90-481-6313-7 ISBN 978-94-017-0105-1 (eBook)
DOI 10.1007/978-94-017-0105-1
Printed on acid-free paper
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© 2003 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 2003.
Softcover reprint ofthe hardcover 1st edition 2003
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Progress in Theoretical Chemistry and Physics
Aseries reporting advances in theoretical molecular and material
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Recent decades have seen the emergence of a novel approach to scientific research,
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v
Progress in Theoretical Chemistry and Physics
in its own right, which can help to test theoretical predictions and mayaiso suggest
improved theories.
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VI
Contents
Preface xm
Contributing Authors XVll
1
Theoretical Chemistry and Physics of Heavy and Superheavy Elements 1
S. Wilson and U. K aldor
1. New Alchemies: from Rutherford to Rutherfordium 2
2. Theoretical Chemistry and Physics of Heavy and Superheavy
Elements 10
2
Basic elements of relativistic quantum mechanics 15
S. Wilson and U. Kaldor
1. Introduction 16
2. The Fundamentals of Relativistic Electronic Structure Theory 18
2.1 The Dirac Equation 20
2.2 The Dirac Matrices 22
2.3 The Dirac Spectrum 27
2.4 Many-Body Systems and Operators 29
2.5 The Electron-Electron Interaction 30
2.6 The Furry Bound-State Interaction Picture of Quantum
Electrodynamics 32
3. The algebraic approximation 34
3.1 Non-relativistic Finite Basis Set Approximations 34
3.2 The Dirac Equation in the Algebraic Approximation 35
3.3 The Matrix Dirac-Hartree-Fock Approximation 39
3.4 A Digression: Finite Nuclear Models 42
3.5 Electron correlation, many-body perturbation theory,
and the no virtual pair approximation 42
3.6 Beyond the no virtual pair approximation 44
4. Summary and Conclusions 48
vii
Vlll HEAVY AND SUPERHEAVY ELEMENTS
3
The Chemistry of the Heaviest Elements 55
V. Pershina and D.C. Hoffman
1. Introduction 56
1.1 Production and identification of the heaviest elements.
A historical overview 56
1.2 Role of chemical studies 60
2. Relativistic effects in the chemistry of the heaviest elements 62
2.1 Relativistic effects on atomic electronic shells 62
2.2 Relativistic quantum chemical calculations 66
3. Predictions of chemical properties 69
3.1 Atomic properties 69
3.2 Properties of gas-phase compounds of elements 104 through
108 73
3.3 Solution chemistry of elements 104, 105 and 106 79
4. One-atom-at-a-time chemistry 86
4.1 Experimental techniques 86
4.2 Results of gas-phase chemistry experiments 89
4.3 Results of solution chemistry experiments 96
5. Prospects for chemical studies of elements heavier than 108 101
5.1 Production of longer-lived isotopes 101
5.2 Theoretical predictions of chemical properties 102
5.3 Experimental investigations and plans 106
6. Summary 107
4
Core and valence electron distributions in heavy elements by x-ray 115
and electron spectroscopy
C. Bonnelle
1. Basic principles of electron and x-ray spectroscopy 118
1.1 General 118
1.2 Interactions with the probe particles 120
1.3 Photoemission 122
1.4 Discrete x-ray emission 123
1.5 Auger emission 125
1.6 Com'plementarity between the different core spectro-
scoples 126
2. Binding energies 127
2.1 Atomic effects 127
2.2 Effects due to the surrounding 131
3. Transitions between localized states 133
3.1 X-ray normal emissions and their satellites 133
3.1.1 Mn K emission spectrum 136
3.1.2 Rare earth x-ray emissions 139
3.1.3 Uranium x-ray emissions 139
3.2 Core photoemission 141
4. X-ray excited states 147
4.1 f states 147
4.1.1 Creation of the x-ray excited states 148
4.1.2 Decay of the x-ray excited states 150
4.1.3 Lanthanum 3d and 4d emissions 151
4.1.4 Erbium 3d emission 154
Contents IX
4.1.5 Uranium 3d, 4d and 5d emissions 154
4.1.6 Plutonium 3d emission 155
4.1.7 Interaction with astate continuum 156
4.2 d states 157
4.3 Discussion 158
5. Valence states in solids 159
5.1 Elements with s and p valence electrons 161
5.2 Transition elements 163
5.3 Lanthanides and Actinides 165
5
Four-component electronic structure methods for atoms 171
Uzi Kaldor, Ephraim Eliav, and Arie Landau
1. Basic Equations 173
1.1 The relativistic Hamiltonian 173
1.2 The one-electron equation 175
1.3 SCF calculations 177
2. Incorporation of Electron Correlation 177
2.1 The Fock-space coupled-cluster method 178
2.2 The intermediate Hamiltonian coupled cluster method 180
3. Applications 182
3.1 Ionization potentials of alkali atoms 183
3.2 Gold and eka-gold (E111): Local maximum ofrelativis-
tic effects 184
3.3 The j2 levels of Pr3+: Importance of dynamic correla-
tion 187
3.4 Ground state of rutherfordium - interplay of relativity
and correlation 189
3.5 Eka-Iead (element 114) - an island of stahility? 191
3.6 Element 118 - can a rare gas have positive electron
affinity? 195
3.7 Eka-actinium (E121) - when is the Breit term impor-
tant? 196
3.8 Electron affinities of alkali atoms - selection of P space 196
3.9 Electron affinities in group 13 - what ahout Ga? 200
3.10 Heavy atom electron affinities - multiple stahle anionic
states 201
3.11 Properties other than energy 202
4. Summary and Conclusion 203
6
Four-component electronic structure methods for moleeules 211
T. Saue and L. Visscher
1. The Hamiltonian 213
1.1 The one-electron part 214
1.1.1 The Dirac equation in an electromagnetic field 214
1.1.2 Time reversal symmetry 218
1.1.3 Charge conjugation symmetry 222
1.1.4 Towards the non-relativistic limit 223
1.2 The two-electron part 225
1.3 Second quantization 227
2. Variational procedures 228
