THE EFFECTS OF RELATIVITY IN ATOMS, MOLECULES, AND THE SOLID STATE
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1 THE EFFECTS OF RELATIVITY IN ATOMS, MOLECULES, AND THE SOLID STATE
2 THE EFFECTS OF RELATIVITY IN ATOMS, MOLECULES, AND THE SOLID STATE Edited by S. Wilson Rutherford Appleton Laboratory Oxfordshire, United Kingdum 1. P. Grant Uniuersity of Oxford Oxford, Uniled Kingdom aud B. L. Gyorffy Universily of Brislol Brislo/, United Kingdom SPRINGER SCIENCE+BUSINESS MEDIA, llc
3 Llbrarv of Congress Catalog lng-ln-publ leat Ion Data The Effects of relatlvity 1n atoms, oolecules, and the solid state I edlted by S. WIIson, I.P. Grant, and B.L. Gyorffy. p. c. "Proceedlngs of a.eetlng on the effects of relatlvity In atoms, molecules, and the solid state, held March 30-Aprll 1, 1990, In Ab lngdon, Oxfordsh 1 re, Un I ted K 1 ngdom "--T. p. verso. Inc I udes b I b li ograph 1cal references and Index. ISBN ISBN (ebook) DOI / Atomic structure--congresses, 2. Molecular structure -Congresses. 3. Solid state physlcs--congresses. 4. Solid state chemlstry--congresses. 5. Reiativity (PhYSics)--Congresses. 1. WIIson, S, (Stephen), II. Grant, 1. P. III. GyiirffY, B. L. QC172.E '.1--dc CIP Proceedings of a meeting on the Effects of Relativity in Atoms, Molecules, and the Solid State, held March 30-ApriI 1, 1990, in Abingdon, Oxfordshire, United Kingdom ISBN Springer Science+Business Media New York Originally published by Plenum Press, New York in 1991 Softcover reprint of the hardcover 1st edition 1991 AII rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher
4 Preface Recent years have seen a growing interest in the effects of relativity in atoms, molecules and solids. On the one hand, this can be seen as result of the growing awareness of the importance of relativity in describing the properties of heavy atoms and systems containing them. This has been fueled by the inadequacy of physical models which either neglect relativity or which treat it as a small perturbation. On the other hand, it is dependent upon the technological developments which have resulted in computers powerful enough to make calculations on heavy atoms and on systems containing heavy atoms meaningful. Vector processing and, more recently, parallel processing techniques are playing an increasingly vital role in rendering the algorithms which arise in relativistic studies tractable. This has been exemplified in atomic structure theory, where the dominant role of the central nuclear charge simplifies the problem enough to permit some prediction to be made with high precision, especially for the highly ionized atoms of importance in plasma physics and in laser confinement studies. Today's sophisticated physical models of the atom derived from quantum electrodynamics would be intractable without recourse to modern computational machinery. Relativistic atomic structure calculations have a history dating from the early attempts of Swirles in the mid 1930's but continue to provide one of the primary test beds of modern theoretical physics. In. non-relativistic molecular structure calculations the use of basis set expansion techniques is almost mandatory. Although it has been known since the work of Kim in the late 1960's that there are problems associated with the use of basis set expansion techniques in relativistic electronic structure calculations, these difficulties have only recently been resolved. By affording a firm foundation for the ab initio treatment of molecules containing heavy atoms and the interactions between them these developments open up new horizons for modern theoretical chemistry. Relativistic quantum chemistry has a vast range of potential applications in both the academic and the commercial sectors in fields as diverse as catalysis and pharmacology, molecular electronics and molecular biology. However, relativistic electronic structure calculations for molecules will remain demanding for some time to come both in the requirement for more efficient and reliable numerical methods and algorithms, and for the computer resources which these methods require. Relativistic solid-state calculations will be just as demanding. In. solid-state theory the emphasis has until now been more on deriving physically intuitive approximation schemes which seem tractable. The consensus which has enabled atomic and molecular physicists and theoretical chemists to build general purpose models has, so far, not existed amongst solid-state theorists. This volume records the proceedings of a meeting on "The Effects of Relativity in Atoms, Molecules and the Solid State" held under the auspices of three of the Science and Engineering Research Council's Collaborative Computational Projects : Project 1 - v
5 Electron correlation in molecules, Project 2 - Continuum states of atoms and molecules, and Project 9 - The electronic structure of solids. The meeting was held at The Coseners House, Abingdon, Oxfordshire, over the weekend 30th March - 1st April, July 1990 s. Wilson I.P. Grant B.L. Gyorffy vi
6 Contents Relativistic Effects on Periodic Trends P.Pyykko ATOMS Relativistic Atomic Structure and Electron-Atom Collisions I.P. Grant On the Accuracy of Oscillator Strengths B.c. Fawcett Atomic Structure Calculations in Breit-Pauli Approximation W. Eissner Relativistic Calculations of Parity Non-Conserving Effects in Atoms A.c. Hartley and P.G.H. Sandars High Precision Relativistic Atomic Structure Calculations Using the Finite Basis Set Approximation H.M. Quiney Relativistic Calculations of Electron Impact Ionisation Cross-Sections of Highly Charged Ions D.L. Moores MOLECULES Nonsingular Relativistic Perturbation Theory and Relativistic Changes of Molecular Structure W.H.E. Schwarz, A. Rutkowski and G. Collignon Basis Set Expansion Dirac-Fock SCF Calculations and MBPT Refinement Y. Ishikawa Comments Polyatomic Molecular Dirac-Hartree-Fock Calculations with Gaussian Basis Sets K.G. Dyall, K. Fregri, Jr. and P.R. Taylor vii
7 Open Shell Relativistic Molecular Dirac-Hartree-Fock SCF-Program O. Visser, PJ.c. Aerts and L. Visscher General Contraction in Four-Component Relativistic Hartree-Fock Calculations L. Visscher, P.J.c. Aerts and O. Visser Accurate Relativistic Dirac-Fock and MBPT Calculations on Argon with Basis Sets of Contracted Gaussian Functions Y. Ishikawa and R.C. Binning, Jr. Comments Relativistic Many-Body Perturbation Theory of Atomic and Molecular Electronic Structure S. Wilson SOLID STATE Relativistic Density-Functional Theory for Electrons in Solids 255 B.L. Gyorffy, J.B. Staunton, H. Ebert, P. Strange and B. Ginatempo Influence of Relativistic Effects on the Magnetic Moments and Hyperfine Fields of 5d-Impurity Atoms Dissolved in Ferromagnetic Fe 275 H. Ebert, B. Drittler, R. Zeller and P.H. Dederichs Relativistic Spin-Polarized Density-Functional Theory: Simplified Method for Fully Relativistic Calculations 285 P. Cortona Theory of Magnetocrystalline Anisotropy 295 J. Staunton, P. Strange, B.L. Gyorffy, M. Matsumoto, J. Poulter, H. Ebert and N.P. Archibald The Spin Polarized Photoemission from Non-Magnetic Metals 319 B. Ginatempo and B.L. Gyorffy Theory of Magnetic X-Ray Dichroism 333 H. Ebert, B. Drittler, P. Strange, R. Zeller and B.L. GyorffY Participants 349 Index 351 viii
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