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Neither Physics Nor Chemistry Transformations: Studies in the History of Science and Technology Jed Z Neither Physics nor Chemistry Transformations: Studies in the History of Science and Technology Jed Z. Buchwald, general editor Red Prometheus: Engineering and Dictatorship in East Germany, 1945– 1990 , Dolores L. Augustine A Nuclear Winter ’ s Tale: Science and Politics in the 1980s , Lawrence Badash Jesuit Science and the Republic of Letters , Mordechai Feingold, editor Ships and Science: The Birth of Naval Architecture in the Scientifi c Revolution, 1600 – 1800 , Larrie D. Ferreiro Neither Physics nor Chemistry: A History of Quantum Chemistry , Kostas Gavroglu and Ana Sim õ es H.G. Bronn, Ernst Haeckel, and the Origins of German Darwinism: A Study in Translation and Trans- formation , Sander Gliboff Isaac Newton on Mathematical Certainty and Method , Niccol ò Guicciardini Weather by the Numbers: The Genesis of Modern Meteorology , Kristine Harper Wireless: From Marconi ’ s Black-Box to the Audion , Sungook Hong The Path Not Taken: French Industrialization in the Age of Revolution, 1750 – 1830 , Jeff Horn Harmonious Triads: Physicists, Musicians, and Instrument Makers in Nineteenth-Century Germany , Myles W. Jackson Spectrum of Belief: Joseph von Fraunhofer and the Craft of Precision Optics , Myles W. Jackson Lenin’s Laureate: Zhores Alferov ’ s Life in Communist Science , Paul R. Josephson Affi nity, That Elusive Dream: A Genealogy of the Chemical Revolution , Mi Gyung Kim Materials in Eighteenth-Century Science: A Historical Ontology , Ursula Klein and Wolfgang Lef è vre American Hegemony and the Postwar Reconstruction of Science in Europe , John Krige Conserving the Enlightenment: French Military Engineering from Vauban to the Revolution , Janis Langins Picturing Machines 1400 – 1700 , Wolfgang Lef è vre, editor Heredity Produced: At the Crossroads of Biology, Politics, and Culture, 1500– 1870 , Staffan M ü ller-Wille and Hans-J ö rg Rheinberger, editors Secrets of Nature: Astrology and Alchemy in Early Modern Europe , William R. Newman and Anthony Grafton, editors Historia: Empiricism and Erudition in Early Modern Europe , Gianna Pomata and Nancy G. Siraisi, editors Nationalizing Science: Adolphe Wurtz and the Battle for French Chemistry , Alan J. Rocke Islamic Science and the Making of the European Renaissance , George Saliba Crafting the Quantum: Arnold Sommerfeld and the Practice of Theory, 1890 – 1926 , Suman Seth The Tropics of Empire: Why Columbus Sailed South to the Indies , Nicol á s Wey G ó mez Neither Physics nor Chemistry A History of Quantum Chemistry Kostas Gavroglu and Ana Sim õ es The MIT Press Cambridge, Massachusetts London, England © 2012 Massachusetts Institute of Technology All rights reserved. No part of this book may be reproduced in any form by any electronic or mechanical means (including photocopying, recording, or information storage and retrieval) without permission in writing from the publisher. For information about special quantity discounts, please email [email protected] This book was set in Stone Sans and Stone Serif by Toppan Best-set Premedia Limited. Printed and bound in the United States of America. Library of Congress Cataloging-in-Publication Data Gavroglu, Kostas. Neither physics nor chemistry : a history of quantum chemistry / Kostas Gavroglu and Ana Sim õ es. p. cm. — (Transformations : studies in the history of science and technology) Includes bibliographical references and index. ISBN 978-0-262-01618-6 (hardcover : alk. paper) 1. Quantum chemistry — History. I. Sim õ es, Ana. II. Title. QD462.G38 2012 541 ′.28 — dc22 2011006506 Photographs of Linus Pauling at the blackboard and the 1948 Colloque published in this book are from the Ava Helen and Linus Pauling Papers, Special Collections, Oregon State University. 10 9 8 7 6 5 4 3 2 1 Contents Preface vii Introduction 1 1 Quantum Chemistry qua Physics: The Promises and Deadlocks of Using First Principles 9 2 Quantum Chemistry qua Chemistry: Rules and More Rules 39 3 Quantum Chemistry qua Applied Mathematics: Approximation Methods and Crunching Numbers 131 4 Quantum Chemistry qua Programming: Computers and the Cultures of Quantum Chemistry 187 5 The Emergence of a Subdiscipline: Historiographical Considerations 245 Notes 263 Bibliography 287 Index 335 Preface The Windows In these dark rooms where I live out empty days, I circle back and forth trying to fi nd the windows. It will be a great relief when a window opens. But the windows are not there to be found — or at least I cannot fi nd them. And perhaps it is better that I don’ t fi nd them. Perhaps the light will prove another tyranny. Who knows what new things it will expose? Constantine P. Cavafy (1863 – 1933). Cavafy lived most of his life in Alexandria, Egypt, and wrote his poetry in Greek. (From: Edmund Keeley. C.P. Cavafy. Copyright © 1975 by Edmund Keeley and Philip Sherrard. Reprinted by permission of Princeton University Press.) All Is Symbols and Analogies Ah, all is symbols and analogies! The wind on the move, the night that will freeze, Are something other than night and a wind. Shadows of life and of shiftings of mind. Everything we see is something besides The vast tide, all that unease of tides, Is the echo of the other tide — clearly Existing where the world there is is real Everything we have’ s oblivion. The frigid night and the wind moving on — These are shadows of hands, whose gestures are the Illusion which is this illusion ’ s mother Fernando Pessoa (1888 – 1935) (November 9, 1932, excerpt from notes for a dramatic poem on Faust). Pessoa lived mostly in Lisbon, Portugal, but spent part of his youth in Durban, South Africa. He wrote in Portuguese and English and used several heteronyms. (From: E.S. Schaffer, ed. Comparative Criticism, Volume 9, Cultural Perceptions and Literary Values [University of East Anglia, CUP, 1987]. Copyright © 1987 Cambridge University Press. Reprinted by permission of Cambridge University Press.) viii Preface Like many other books, this book has had a long period of gestation. We fi rst met years ago on the other side of the Atlantic, in 1991 in Madison, Michigan, when one of us was writing the scientifi c biography of Fritz London and the other completing her Ph.D. thesis about the emergence of quantum chemistry in the United States. Since then, on and off, we have been discussing various aspects of quantum chemis- try — of a subdiscipline that is not quite physics, not quite chemistry, and not quite applied mathematics and that was referred to as mathematical chemistry, subatomic theoretical chemistry, quantum theory of valence, molecular quantum mechanics, chemical physics, and theoretical chemistry until the community agreed on the des- ignation of quantum chemistry, used in all probability for the fi rst time by Arthur Erich Haas (1884 – 1941), professor of physics at the University of Vienna, in his book Die Grundlagen der Quantenchemie (1929). Progressively, we became more and more intrigued by the emergence of a culture for doing quantum chemistry through the synthesis of the various traditions of chem- istry, physics, and mathematics that were creatively meshed in different locales. We decided to look systematically at the making of this culture — of its concepts, its prac- tices, its language, its institutions — and the people who brought about its becoming. We discuss the contributions of the physicists, chemists, and mathematicians in the emergence and establishment of quantum chemistry since the 1920s in chapters 1, 2, and 3. Chapter 4 deals with the dramatic changes brought forth to quantum chemistry by the ever more intense use of electronic computers after the Second World War, and we continue our story until the early 1970s. To decide when one stops researching, to decide what not to include is always a decision involving a dose of arbitrariness. Nec- essarily and naturally, a lot has been left out. The fi rst work that had convincingly shown that quantum mechanics could suc- cessfully deal with one of the most enigmatic problems in chemistry was published in 1927. It was a paper by Walter Heitler and Fritz London, who discussed the bonding of two hydrogen atoms into a molecule within the newly formulated quantum mechanical framework. Thus, we start our narrative after the advent of quantum mechanics and try to read the unevenly successful attempts to explain the nature of bonds that were made by different communities of specialists within different insti- tutional settings and supported by different methodological and ontological choices. The narrative about the development of quantum chemistry should not be consid- ered only as the history of the way a particular (sub)discipline was formed and estab- lished. It is, at the same time, “ part and parcel ” of the development of quantum mechanics. The formation of the particular (sub)discipline does, indeed, have a relative autonomy, with respect to the development of quantum mechanics, but this kind of autonomy can only be properly appreciated when it is embedded within the overall framework of the development of quantum mechanics. The history of quantum mechanics is, certainly, not an array of milestones punctuated by the “ successes ” of Preface ix the applications of quantum mechanics. Such applications should not only be con- sidered either as extensions of the limits of validity of quantum mechanics or as “ instances ” contributing to its further legitimation, as in any such “ application ” we can think of — be it nuclear physics, quantum chemistry, superconductivity, superfl uid- ity, to mention a few — new concepts were introduced, new approximation methods were developed, and new ontologies were proposed. The development of quantum mechanics “ proper ” and “ its applications ” are historically a unifi ed whole where, of course, each preserves its own relative autonomy. In a couple of years after the amazingly promising papers of Heitler, London, and Friedrich Hund, Paul Adrien Maurice Dirac made a haunting observation: that quantum mechanics provided all that was necessary to explain problems in chemistry, but at a cost.
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