Chemical Physics of Free Molecules PDF
Preview Chemical Physics of Free Molecules
CHEMICAL PHYSICS OF FREE MOLECULES CHEMICAL PHYSICS OF FREE MOLECULES Norman H. March Oxford Univenity Oxford, England and Joseph F. Mucci Vassar College Poughkeepsie, New York Springer Science+Business Media, LLC Library of Congress Cataloging-in-Publication Data March, Norman H. (Nor~an Henry), 1927- Chemical physics of free molecules I Norman H. March ana ~oseph F. Mucc i. p. cm. Includes bibliographical references and index. 1. Chemical bonds. 2. Intermolecular forces. 3. Molecules. I. Mucci, Joseph F. II. Title. 00461. M26 1994 541.2'24--dc20 93-24193 CIP ISBN 978-1-4757-9648-3 ISBN 978-1-4757-9646-9 (eBook) DOI 10.1007-978-1-4757-9646-9 C 1993 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1993. Softcover reprint of the hardcover 1s t edition 1993 All 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 PREFACE The aim of this book is to provide a basic treatment of both electronic and nuclear motions in molecules, which is suitable for chemical physicists and for chemists. The book may also be of use, as an introduction to molecules, to materials scientists who wish to employ the methods of quantum chemistry to study con densed molecular matter, though the present work is almost exclusively about the gas phase. * The level is for advanced undergraduate students and postgraduates. From the outset, attention is focused on the molecule, with its attendant multinuclear character. Thus, the simplest problem treated in the body of the text is the hydrogen molecule ion. However, some background is presented in the Appendixes, regarding the electronic structure of atoms and their binding energies. The main tool employed in treating electronic behavior is the variation method. While this is widely used in current undergraduate texts for dealing with wave functions, a unique feature of the present account is that it is also used, within the framework of the "inhomogeneous electron gas,"t to treat the ground state electron density. Both variational approaches, wave function and electron density, are brought to full fruition when used to establish a self-consistent field. This concept, going back to Hartree, is a recurring theme. We therefore elaborate a little on its meaning immediately below. Only in the one problem of the H~ ion referred to above do we have a situ.ation of chemical interest where electron repulsion does not occur. It is our view in this work that the existence of localized chemical bonding is a rather direct manifestation of the importance of the correlated motion of electrons, both because the electrons have spin, and parallel spin electrons avoid one another as a consequence of the Pauli Exclusion Principle; and also because all electrons, whether with parallel or antiparallel spins, avoid one another by virtue of Cou lomb repulsion. Nevertheless, certain properties of molecules, most importantly the ground state electron density (the pioneers having been Thomas, Fermi, and Dirac), can be calculated by one-electron (orbital) methods, provided the electron correlation, both Pauli principle and Coulombic repulsion, is built into a suitable self-consistent field in which the electrons move independently. This recognition means that the "conflict" which sometimes appeared historically to exist between orbital methods on the one hand and chemical, valence bond, methods on the *A few examples taken from solids and liquids have been used to illustrate points concerned with chemical bonding in free molecules. tFor the reader who becomes deeply interested in the electron density description, advanced accounts can be found in The Theory of the Inhomogeneous Electron Gas, S. Lundqvist and N. H. March, eds., Plenum Press, New York (1983); Density Functional Theory of Atoms and Molecules by R. G. Parr and W. Yang, Oxford University Press (1989); and Electron Density Theory of Atoms and Molecules by N. H. March, Academic Press, New York (1992). v other is only apparent. For some purposes, orbital methods are very convenient VI Preface and can be formulated, at least in principle, exactly. For specified (i.e., fixed) nuclear positions, knowledge of the ground state electron density suffices (via the so-called Hellmann-Feynman theorem described in the Appendix) to calculate the forces on all nuclei, which are evidently needed to discuss vibrational degrees of freedom. Though this approach is not explicitly utilized in the present work (see Chapter 3 for an alternative approach to molecu lar force fields), it serves to highlight further the long-term importance for chemical physics of the ground state electron density. * While we are both practicing theorists, we have also sought in our presenta tion here to emphasize the crucial interplay between experiment and theory in this subject. This, we believe, is made especially clear in Chapters 1, 5, and 7, the last constituting a brief introduction to the now vast field of chemical reactions. Finally we note (i) that much of the material presented here has been used in undergraduate courses at Vassar College and at Oxford University, and (ii) that if our book should find favor with university teachers of such courses, we shall be most grateful for constructive criticism, to which we shall do our best to respond if the opportunity arises in the future. We gratefully acknowledge the encouragement and help of members of the Editorial Staff at Plenum; namely, Amelia McNamara, Laura Troup, and Barbara Sonnenschein. We especially want to thank our copyeditor, Evelyn Grossberg, for her understanding and expertise. In addition, we thank Marilyn Bontempo for the production of the art work. Norman H. March Joseph F. Mucci *In principle a directly observable property, unlike the many-electron wave function, via X-ray or electron diffraction experiments. ACKNOWLEDGMENTS We gratefully acknowledge permission to reproduce figures and tables from other sources as follows: Chapter 1 Figure 1.2. Chemical Bonding Clarified Through Quantum Mechanics by G. C. Pimentel and R. D. Spratley, Holden-Day Inc., San Francisco (1969). Reprinted by permission of the authors, the copyright owners. Figure 1.4. High Resolution Spectroscopy by J. M. Hollas, Butterworth!fPublish ers (1982). Reprinted by permission of Butterworth-Heinemann Publishers. Figure 1.5. ECSA Applied to Free Molecules by K. Siegbahn, C. Nordling, G. Johansson, P. F. Heden, K. Hamerin, U. Gelius, T. Bergmark, L. O. Worme, R. Manne, and Y. Baer, copyright (c) 1969 by North-Holland Publishing Co., Amsterdam. Reprinted by permission of Elsevier Science Publishers. Figures 1.7 and 1.8. Quanta by P. W. Atkins, 2nd Ed., Oxford University Press, Oxford (1991). Reprinted by permission of Oxford University Press. Figures 1.9 and 1.10. H. L. Chen and C. B. Moore, J. Chem. Phys. 54, 4072 (1971). Reprinted by permission of the American Institute of Physics and the authors. Figure 1.11. Molecular Structure and Dynamics by W. H. F1ygare, Prentice-Hall Inc., Englewood Cliffs, N.J. (1978). Reprinted by permission of Ruth M. Flygare, the current copyright owner. Figure 1.12. Modern Spectroscopy by J. M. Hollas, copyright (c) 1987 by John Wiley and Sons Ltd., Chichester. By permission of copyright owner. Tables 1.1 and 1.4. Reprinted from The Nature of the Chemical Bond and the Structure of Molecules and Crystals: An Introduction to Modern Structural Chem istry 3rd. Ed. by Linus Pauling. 3rd edition copyright (c) 1960 by Cornell Univer sityPress. Used by permission of the publisher, Cornell University Press. Tables 1.2 and 1.3. Chemical Structure and Bonding by R. L. DeKock and H. B. Gray, Benjamin/Cummings Publishing Co., Menlo Park, CA. (1980). Reprinted by permission of the current copyright holder, Roger DeKock. Table 1.5. Chemical Constitution, 2nd. Ed. by J. A. A. Ketelaar, Elsevier Science Publishers, Amsterdam, 1958. Reprinted by permission of Elsevier Science Publi shers and the author. Table 1.6. J. L. Hollenberg, J. Chem. Educ. 47, 2 (1970). Reprinted by permission of the Division of Chemical Education of the American Chemical Society. vii V111 Chapter 2 Acknowledgments Figure 2.4. Physical Chemistry by R. S. Berry, S. A. Rice, and J. Ross. Copyright (c) 1980 by John Wiley and Sons, Inc., New York. Reprinted by permission of John Wiley and Sons, Inc. Figures 2.5, 2.7, 2.9, 2.10, 2.11, and 2.13. Coulson's Valence, 3rd Ed. by R. McWeeny, Oxford University Press, Oxford, 1979. Reprinted by permission of Oxford University Press. Figure 2.14. R. F. W. Bader, 1. Keaveney, and P. E. Cade, J. Chem. Phys. 47, 3381 (1967). Reprinted by permission of the American Institute of Physics and the authors. Table 2.2. Wave Mechanics for Chemists by C. W. N. Cumper, Academic Press Inc., 1966. Reprinted by permission of the current copyright owner Butterworth Heinemann Ltd. and the author. Table 2.5. The Structure of Small Molecules by W. J. Orville-Thomas, Elsevier Science Publishers, 1966. Reprinted by permission of the author and the current copyright owner. Chapter 3 Figures 3.1,3.9,3.10,3.15,3.17, and Table 3.4. The Forces Between Molecules by M. Rigby, E. B. Smith, W. A. Wakeham, and G. C. Maitland, Oxford Univer sity Press, Oxford, 1986. Reprinted by permission of Oxford University Press. Figure 3.2. Introduction to Physical Chemistry by Arthur M. Lesk, (c) 1982. Reprinted by permission of Prentice-Hall, Inc., Englewood Cliffs, New Jersey. Figure 3.8. M. Ross, H. K. Mao, P. M. Bell, and J. A. Xu, J. Chem. Phys. 85, 1028 (1986). Reprinted by permission of the American Institute of Physics and the authors. Figure 3.11. Bonding Theory by D. J. Royer, McGraw-Hill, New York, 1986. Copyright (c) 1968 by McGraw-Hill Inc. Reprinted by permission by McGraw Hill, Inc. Figure 3.12. Advanced Physical Chemistry by J. C. Davis, Ronald Press Co., N.Y., 1965. Reprinted by permission of John Wiley and Sons, Inc., the current copyright owners. Figure 3.13. Kinetic Theory of Gases by W. Kauzmann, W. A. Benjamin Inc., New York, 1966. Reprinted by permission of Benjamin/Cummings Publishing Co. Figures 3.14 and 3.16. Physical Chemistry, 2nd Ed. by P. W. Atkins. Copyright (c) 1982 by P. W. Atkins. Reprinted by permission of W. H. Freeman and Company, New York. Figure 3.18. P. A. Egelstaffand F. Barocchi, Phys. Lett. 3, 313 (1985). Reprinted by permission of Elsevier Science Publishers and the authors. Table 3.5. The Chemical Bond, 2nd Ed. by J. N. Murrell, S. F. A. Kettle, and J. M. Tedder. Copyright (c) 1985 by John Wiley and Sons Ltd. Reprinted by permission of John Wiley and Sons Ltd. Chapter 4 IX Figure 4.2. N. L. Allan, D. L. Cooper, C. G. West, P. J. Grout, and N. H. Acknowledgments March, J. Chem. Phys. 83, 239 (1983). Reprinted by permission of the American Institute of Physics and the authors. Figures 4.3 and 4.4. J. F. Mucci and N. H. March, J. Chem. Phys. 71, 5270 (1979). Reprinted by permission of the American Institute of Physics. Chapter 5 Figure 5.1. Fundamentals of Molecular Spectroscopy by C. M. Banwell, McGraw-Hill Book Co. Reprinted by permission of McGraw-Hill, Inc. Figure 5.5. Modern Spectroscopy by J. M. Hollas, 1987. Copyright (c) by John Wiley and Sons Ltd., Chichester. By permission of the copyright owner. Figures 5.6, 5.7, and 5.10. High-Resolution Spectroscopy by J. M. Hollas, Butter worths Publishers (1982). Reprinted by permission of Butterworth-Heinemann Publishers. Figure 5.11. E. A. Ballik and D. A. Ramsay, Astrophys. J. 137, 84 (1963). Reprinted by permission of the publisher and the authors. Figure 5.13. L. Karlsson, K. Mattsson, R. Jadrny, T. Bergmark, and K. Siegbahn, Physica Scripta 14, 230 (1976). Reprinted by permission of the Royal Swedish Academy of Sciences. Figure 5.14. Molecular Structure and Dynamics by W. H. Flygare, Prentice-Hall Inc., Englewood Cliffs, New Jersey, 1978. Reprinted by permission of Ruth M. Flygare the current copyright owner. Figure 5.17. Spectroscopy and Structure by R. N. Dixon, John Wiley and Sons Inc., 1965. Reprinted by permission of Chapman and Hall, London the current copyright owner. Figure 5.18. A. A. Bothner-By and C. Naar-Co1in, Ann. N. Y. Acad. Sci. 70, 833 (1958). Reprinted by permission of the New York Academy of Science and the authors. Figure 5.22. Quantum Chemistry by J. P. Lowe, copyright (c) Academic Press Inc., New York, 1978. Reprinted by permission of Academic Press and the author. Chapter 6 Figure 6.3. Molecular Photoelectron Spectroscopy by D. W. Turner, C. Baker, A. D. Baker, and C. R. Brund1e, Copyright (c) 1970 by John Wiley and Sons Ltd. Reprinted by permission of John Wiley and Sons Ltd. Figures 6.4, 6.15, and 6.30. High Resolution Spectroscopy by J. M. Hollas, Butterworths Publishers, 1982. Reprinted by permission of Butterworth Heinemann Publishers. Figure 6.10. Valence, 2nd Ed, by C. A. Coulson, Oxford University Press, Oxford, 1961. Reprinted by permission of Oxford University Press. Figure 6.27. L. Karlsson, L. Mattson, R. Jadrny, T. Bergmark, and K. Siegbahn, X Acknowledgments Physica Scripta, 230 (1976). Reprinted by permission of the Royal Swedish Academy of Sciences. Figure 6.29. M. A Coplan, J. H. Moore, and J. A Tossell, J. Chem. Phys. 68, 329 (1978). Reprinted by permission of the American Institute of Physics and the authors. Chapter 7 Figures 7.5, 7.6, 7.7, 7.8, 7.9, and Tables 7.2, 7.3, and 7.4. Physical Organic Chemistry by K. B. Wiberg. John Wiley and Sons Inc., New York 1964. Reprinted by permission of the author the current copyright owner. Figures 7.10, 7.11, 7.12, 7.13, 7.14, 7.15, 7.16, and 7.17, 7.19, 7.20. Quantum Chemistry by J. P. Lowe, Academic Press 1978. Reprinted by permission of the publisher and author. Figure 7.18. Molecular Orbital Theory by A Streitwieser Jr., John Wiley and Sons Inc., N.Y., 1961. Reprinted by permission of the author the cum,nt copyright owner. Figure 7.21. R. N. Zare and R. B. Bernstein, Physics Today, Vol. 33, No. 11 (1980). Reprinted by permission of the American Institute of Physics and the authors. Figure 7.22 and Table 7.6. Chemical Kinetics 3rd Ed. by Keith J. Laidler. Copy right (c) 1987 by Harper and Row Publishers, Inc., N.Y. Reprinted by permission of Harper Collins Publishers. Table 7.5. Quanta, 2nd Ed. by P. W. Atkins, Oxford University Press, Oxford, 1991. Reprinted by permission of Oxford University Press. . Appendix Figure A.5. C. A Coulson and I. Fischer, Philosophical Magazine (London) 40, 386 (1949). Reproduced with permission of the publisher, Taylor and Francis, Inc. Figure A9. L. S. Bartell and L. O. Brockway, Phys. Rev. 90, 833 (1953). Reprinted by permission of the American Institute of Physics and the authors. Figures A.ll, A.12, and A. 13. J. A. Alonso and N. H. March, Chem. Phys. 76, 121 (1983). Reprinted by permission of Elsevier Science Publishers BV and the authors. Figures A.14. K. E. Banyard and N. H. March, Acta. Cryst. 9, 385 (1956). Reprinted by permission of International Union of Crystallography. Figures A.20, A2l, and A22 and Table A. 1. Quantum Chemistry by J. P. Lowe. Copyright (c) Academic Press, Inc.,·N.Y. 1978. Reprinted by permission of the publishers and the author. Figures A.23 and A.24 and Tables A.3 through A.8. M. Raimondi, M. Simonetta, and J. Gerratt, Chem. Phys. Letts. 77, 12 (1981). Reprinted by permis sion of Elsevier Science Publishers BV and the authors.
The list of books you might like
