Quantum Chemistry: The Development of Ab Initio Methods in Molecular Electronic Structure Theory

DOVER BOOKS ON CHEMISTRY

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RADIOACTIVE SUBSTANCES, Marie Curie. (42550-9)

THE CHEMICAL PHILOSOPHY, Allen G. Debus. (42175-9)

CHEMICAL. MAGIC, Leonard A. Ford. (Second Edition, revised by E. Winston Grundmeier.) (67628-5)

SYMMETRY AND SPECTROSCOPY: AN INTRODUCTION TO VIBRATIONAL AND ELECTRONIC SPECTROSCOPY, Daniel C. Harris and Michael D. Bertolucci. (66144-X)

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ADVENTURES WITH A MICROSCOPE, Richard Headstrom. (23471-1)

CRYSTAL GROWTH IN GELS, Heinz K. Henisch. (68915-8)

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THE DEVELOPMENT OF MODERN CHEMISTRY, Aaron J. Ihde. (64235-6)

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SYMMETRY IN CHEMISTRY, Hans H. Jaffé and Milton Orchin. (42181-3)

CRYSTAL CHEMISTRY AND REFRACTIVITY, Howard W. Jaffe. (69173-X)

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THE DEVELOPMENT OF CHEMICAL PRINCIPLES, Cooper H. Langford and Ralph A. Beebe. (68359-1)

ELEMENTS OF CHEMISTRY, Antoine Lavoisier. (64624-6)

RATES AND EQUILIBRIA OF ORGANIC REACTIONS: As TREATED BY STATISTICAL, THERMODYNAMIC AND EXTRATHERMODYNAMIC METHODS, John E. Leffler and Ernest Grunwald. (66068-0)

THE HISTORICAL BACKGROUND OF CHEMISTRY, Henry M. Leicester. (61053-5) QUANTUM MECHANICS OF MOLECULAR RATE PROCESSES, Raphael D. Levine. (40692-X)

QUANTUM MECHANICS, Albert Messiah. (40924-4)

A SHORT HISTORY OF CHEMISTRY (3RD EDITION), J. R. Partington. (65977-1)

GENERAL CHEMISTRY, Linus Pauling. (65622-5)

ELEMENTARY QUANTUM CHEMISTRY, SECOND EDITION, Frank L. Pilar. (41464-7)

FROM ALCHEMY TO CHEMISTRY, John Read. (28690-8)

ELECTROLYTE SOLUTIONS: SECOND REVISED EDITION, R. A. Robinson and R. H. Stokes. (42225-9)

FIRE: SERVANT, SCOURGE, AND ENIGMA, Hazel Rossotti. (42261-5)

INTRODUCTION TO CRYSTALLOGRAPHY, Donald E. Sands. (67839-3)

QUANTUM MECHANICS IN CHEMISTRY, George C. Schatz and Mark A. Ratner. (42003-5)

MODERN QUANTUM CHEMISTRY: INTRODUCTION TO ADVANCED ELECTRONIC STRUCTURE THEORY, Attila Szabo and Neil S. Ostlund. (69186-1)

THEORY OF THE STABILITY OF LYOPHOBIC COLLOIDS, E. J. W. Verwey and J. Th. G. Overbeek. (40929-5)

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Paperbound unless otherwise indicated. Available at your book dealer, online at www.doverpublications.com, or by writing to Dept. 23, Dover Publications, Inc., 31 East 2nd Street, Mineola, NY 11501. For current price information or for free catalogs (please indicate field of interest), write to Dover Publications or log on to www.doverpublications.com and see every Dover book in print. Each year Dover publishes over 500 books on fine art, music, crafts and needlework, antiques, languages, literature, children’s books, chess, cookery, nature, anthropology, science, mathematics, and other areas.

Manufactured in the U.S.A.

Copyright

Copyright © 1984 Henry F. Schaefer III

All rights reserved.

Bibliographical Note

This Dover edition, first published in 2004, is an unabridged republication of the 1985 reprinting of the work first published by Clarendon Press, Oxford, in 1984.

Library of Congress Cataloging-in-Publication Data

Schaefer, Henry F.

Quantum chemistry : the development of ab initio methods in molecular electronic structure theory / Henry F. Schaefer III.

p. cm.

Originally published: Oxford [Oxfordshire] : Clarendon Press, 1984.

Includes bibliographical references and index.

9780486151410

1. Quantum chemistry. 2. Electronic structure. I. Title.

QD462.S32 2004

541'.28—dc22

2003067441

Manufactured in the United States of America

Dover Publications, Inc., 31 East 2nd Street, Mineola, N.Y. 11501

Table of Contents

DOVER BOOKS ON CHEMISTRY

Title Page

Copyright Page

Preface

Dedication

An incomplete list of landmark papers in ab initio molecular electronic structure methods

1 - E. A. HYLLERAAS

2 - H. M. JAMES & A. S. COOLIDGE

3 - C. M∅LLER & M. S. PLESSET

4 - D. R. HARTREE, W. HARTREE, & B. SWIRLES

5 - M. KOTANI, A. AMEMIYA, E. ISHIGURO, & T. KIMURA

6 - S. F. BOYS

7 - S. F. BOYS

8 - K. RUEDENBERG

9 - C. C. J. ROOTHAAN

10 - G. R. TAYLOR & R. G. PARR

11 - R. G. PARR & B. L. CRAWFORD

12 - J. A. POPLE & R. K. NESBET

13 - H. SHULL & P. O. LÖWDIN

14 - P. O. LÖWDIN

15 - R. K. NESBET

16 - S. F. BOYS, G. B. COOK, C. M. REEVES, & I. SHAVITT

17 - J. MILLER, R. H. FRIEDMAN, R. P. HURST, & F. A. MATSEN

18 - C. L. PEKERIS

19 - P. O. LÖWDIN

20 - R. S. MULLIKEN & C. C. J. ROOTHAAN

21 - A. D. McLEAN

22 - E. R. DAVIDSON

23 - R. E. WATSON

24 - C. C. J. ROOTHAAN

25 - B. J. RANSIL

26 - R. K. NESBET

27 - S. F. BOYS & G. B. COOK

28 - J. M. FOSTER & S. F. BOYS

29 - O. SINANOGLU

30 - I. SHAVITT & M. KARPLUS

31 - E. CLEMENTI

32 - R. M. PITZER & W. N. LIPSCOMB

33 - C. C. J. ROOTHAAN & P. S. BAGUS

34 - H. P. KELLY

35 - C. EDMISTON & K. RUEDENBERG

36 - R. K. NESBET

37 - M. P. BARNETT

38 - S. HAGSTROM & H. SHULL

39 - A. C. WAHL

40 - M. KRAUSS

41 - E. CLEMENTI

42 - S. HUZINAGA

43 - R. K. NESBET

44 - J. M. SCHULMAN & J. W. MOSKOWITZ

45 - P. S. BAGUS

46 - G. DAS & A. C. WAHL

47 - P. F. FOUGERE & R. K. NESBET

48 - J. L. WHITTEN

49 - H. J. SILVERSTONE & O. SINANOGLU

50 - P. E. CADE, K. D. SALES, & A. C. WAHL

51 - S. D. PEYERIMHOFF, R. J. BUENKER, & L. C. ALLEN

52 - C. EDMISTON & M. KRAUSS

53 - J. CIZEK

54 - C. F. BENDER & E. R. DAVIDSON

55 - A. D. McLEAN & M. YOSHIMINE

56 - F. GRIMALDI, A. LECOURT, & C. MOSER

57 - M. YOSHIMINE & A. D. McLEAN

58 - A. A. FROST

59 - E. CLEMENTI & J. N. GAYLES

60 - R. K. NESBET

61 - R. AHLRICHS & W. KUTZELNIGG

62 - K. MOROKUMA & L. PEDERSEN

63 - W. KOLOS & L. WOLNIEWICZ

64 - E. R. DAVIDSON & C. F. BENDER

65 - J. GERRATT & I. M. MILLS

66 - D. NEUMANN & J. W. MOSKOWITZ

67 - C. F. BUNGE

68 - H. F. SCHAEFER & F. E. HARRIS

69 - T. H. DUNNING, W. J. HUNT, & W. A. GODDARD

70 - R. K. NESBET, T. L. BARR, & E. R. DAVIDSON

71 - L. C. SNYDER & H. BASCH

72 - R. C. LADNER & W. A. GODDARD

73 - P. PULAY

74 - U. KALDOR & F. E. HARRIS

75 - C. F. BENDER & E. R. DAVIDSON

76 - R. P. HOSTENY, R. R. GILMAN, T. H. DUNNING, A. PIPANO, & I. SHAVITT

77 - A. K. Q. SIU & E. R. DAVIDSON

78 - C. F. BENDER & H. F. SCHAEFER

79 - D. M. SILVER, K. RUEDENBERG, & E. L. MEHLER

80 - M. D. NEWTON, W. A. LATHAN, W. J. HEHRE, & J. A. POPLE

81 - P. J. BERTONCINI, G. DAS, & A. C. WAHL

82 - H. F. SCHAEFER

83 - A. BUNGE

84 - J. M. SCHULMAN & D. N. KAUFMAN

85 - T. H. DUNNING

86 - H. F. SCHAEFER, D. R. McLAUGHLIN, F. E. HARRIS, & B. J. ALDER

87 - P. J. BERTONCINI & A. C. WAHL

88 - T. H. DUNNING & N. W. WINTER

89 - F. GREIN & T. C. CHANG

90 - W. MEYER

91 - E. CLEMENTI, J. MEHL, & W. VON NIESSEN

92 - H. F. SCHAEFER

93 - S. ROTHENBERG & H. F. SCHAEFER

94 - J. B. ROSE & V. McKOY

95 - B. ROOS

96 - J. A. HORSLEY, Y. JEAN, C. MOSER, L. SALEM, R. M. STEVENS, & J. S. WRIGHT

97 - L. R. KAHN & W. A. GODDARD

98 - W. J. HUNT, P. J. HAY, & W. A. GODDARD

99 - E. CLEMENTI & H. POPKIE

100 - C. F. BENDER, S. V. O’NEIL, P. K. PEARSON & H. F. SCHAEFER

101 - K. RUEDENBERG, R. C. RAFFENETTI, & R. D. BARDO

102 - J. ROSE, T. SHIBUYA, & V. McKOY

103 - W. MEYER

104 - R. C. RAFFENETTI

105 - G. C. LIE, J. HINZE, & B. LIU

106 - R. M. PITZER

107 - I. SHAVITT, C. F. BENDER, A. PIPANO, & R. P. HOSTENY

108 - M. YOSHIMINE

109 - U. KALDOR

110 - M.-M. COUTIERE, J. DEMUYNCK, & A. VEILLARD

111 - S. R. LANGHOFF & E. R. DAVIDSON

112 - P. J. HAY & I. SHAVITT

113 - J. PALDUS

114 - F. SASAKI & M. YOSHIMINE

115 - R. AHLRICHS, H. LISCHKA, V. STAEMMLER, & W. KUTZELNIGG

116 - E. A. McCULLOUGH

117 - C. W. BAUSCHLICHER, D. H. LISKOW, C. F. BENDER, & H. F. SCHAEFER

118 - E. R. DAVIDSON

119 - G. H. F. DIERCKSEN, W. P. KRAEMER, & B. O. ROOS

120 - R. AHLRICHS & F. DRIESSLER

121 - H. F. SCHAEFER & W. H. MILLER

122 - S. R. LANGHOFF & E. R. DAVIDSON

123 - M. DUPUIS, J. RYS, & H. F. KING

124 - P. ROSMUS & W. MEYER

125 - C. E. DYKSTRA, H. F. SCHAEFER, & W. MEYER

126 - L. G. YAFFE & W. A. GODDARD

127 - C. F. BUNGE

128 - I. SHAVITT

129 - W. VON NIESSEN, G. H. F. DIERCKSEN, & L. S. CEDERBAUM

130 - R. P. SAXON & B. LIU

131 - J. E. GREADY, G. B. BACSKAY, & N. S. HUSH

132 - J. A. POPLE, R. KRISHNAN, H. B. SCHLEGEL, & J. S. BINKLEY

133 - R. J. BARTLETT & G. D. PURVIS

134 - P. SIEGBAHN & B. LIU

135 - R. J. BUENKER, S. D. PEYERIMHOFF, & W. BUTSCHER

136 - J. A. POPLE, R. KRISHNAN, H. B. SCHLEGEL, & J. S. BINKLEY

137 - B. R. BROOKS & H. F. SCHAEFER

138 - P. E. M. SIEGBAHN

139 - B. O. ROOS, P. R. TAYLOR, & P. E. M. SIEGBAHN

140 - B. LIU & A. D. McLEAN

141 - R. KRISHNAN, M. J. FRISCH, & J. A. POPLE

142 - B. R. BROOKS, W. D. LAIDIG, P. SAXE, J. D. GODDARD, Y. YAMAGUCHI & H. F. SCHAEFER

143 - R. KRISHNAN, H. B. SCHLEGEL, & J. A. POPLE

144 - B. H. LENGSFIELD

145 - Y. OSAMURA, Y. YAMAGUCHI, P. SAXE, M. A. VINCENT, J. F. GAW, & H. F. SCHAEFER

146 - G. D. PURVIS & R. J. BARTLETT

147 - Y. OSAMURA, Y. YAMAGUCHI, & H. F. SCHAEFER

148 - J. ALMLÖF, K. FAEGRI, & K. KORSELL

149 - V. R. SAUNDERS & J. H. VAN LENTHE

Author Index

Subject Index

A CATALOG OF SELECTED DOVER BOOKS IN SCIENCE AND MATHEMATICS

Preface

More than eleven years ago, the author completed the monograph, The electronic structure of atoms and molecules: a survey of rigorous quantum mechanical results. At the time of publication (1972), most practicing chemists were not aware that the ab initio methods of molecular electronic structure theory were capable of providing reliable predictions of quantities of chemical interest. A number of my colleagues at Berkeley expressed surprise at the time that variational quantum mechanical methods could be applied to systems as large as XeF6, azulene, and the guanine-cytosine base pair. Similar astonishment greeted the notion that for some of the simplest polyatomic molecules (e.g. methylene) theory could successfully challenge the most sophisticated experimental spectroscopic studies.

During the past decade the situation described above has almost entirely reversed itself. In what has been described as the beginning of the ‘Third Age of Quantum Chemistry’ [W. G. Richards, Nature 278, 507 (1979)], there are now literally dozens of cases in which electronic structure theorists have successfully contested the laboratory conclusions of distinguished experimentalists. The specific case Richards describes in the above-cited article is one in which theory and experiment worked closely together to unravel the spectroscopy of triplet acetylene in a manner which would not have been possible by either party working in isolation.

Another sign of the minor chemical revolution that ab initio methods are producing is the fact that a number of highly regarded experimental chemists have more or less abandoned their laboratory research programs in favor of quantum mechanical studies. In most cases this transformation from experiment to theory has been quite successful, since experimentalists appreciate the subtleties of their own laboratory equipment and tend to transfer this healthy caution to the theoretical methods they adopt when going into the ab initio field on a full-time basis.

However, the majority of users of electronic structure theory are no longer professional theoreticians, but rather experimentalists who simply do not have the time to take off a year or two to become experts in the field. And this is precisely the group whose numbers will grow at by far the most rapid rate during the next decade. This phenomenon must be considered simultaneously the greatest triumph and the greatest threat to the integrity of molecular quantum mechanics. The use of the former description should be obvious, since the goal of most electronic structure theorists since 1930 has been the development of methods readily applicable to the broadest range of chemical problems.

Nevertheless, one must concede that there are great perils associated with the application of ab initio methods to chemical problems. When an experimentalist turns in his latest new compound to the departmental n.m.r. facility, at least he is reasonably certain that the output will be an n.m.r. spectrum. He may have to be careful that the n.m.r. spectrum refers to a single compound rather than a mixture, but this is an uncertainty that chemists have