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Erich Hückel (1896-1980): from Physics to Quantum Chemistry

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Erich Hückel (1896-1980): from Physics to Quantum Chemistry ERICH HÜCKEL (1896–1980) BOSTON STUDIES IN THE PHILOSOPHY OF SCIENCE Editors ROBERT S. COHEN, Boston University JÜRGEN RENN, Max Planck Institute for the History of Science KOSTAS GAVROGLU, University of Athens Editorial Advisory Board THOMAS F. GLICK, Boston University ADOLF GRÜNBAUM, University of Pittsburgh SYLVAN S. SCHWEBER, Brandeis University JOHN J. STACHEL, Boston University MARX W. WARTOFSKY†, (Editor 1960–1997) VOLUME 283 For further volumes: http://www.springer.com/series/5710 ERICH HÜCKEL (1896 –1980) From Physics to Quantum Chemistry ANDREAS KARACHALIOS Translated by Ann M. Hentschel 123 Andreas Karachalios Ernst-Reuter-Str. 14 55130 Mainz Germany [email protected] ISBN 978-90-481-3559-2 e-ISBN 978-90-481-3560-8 DOI 10.1007/978-90-481-3560-8 Springer Dordrecht Heidelberg London New York Library of Congress Control Number: 2009939498 © Springer Science+Business Media B.V. 2010 No part of this work 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, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com) To the memory of my friend, Thanos Liarommatis Acknowledgments It is a pleasure for me to thank those persons who lent me their support. David Rowe and Moritz Epple offered guidance and commentary during the growing stages of this work. I thank them heartily for their inspiring ideas and active assistance. I am also especially grateful to W.H. Eugen Schwarz, Hans Sillescu, and Joachim Stocklöv for their valuable and helpful comments. Finally, I’d like to thank the following persons for their efforts: Regina Grimm- Karachalios, Ann M. Hentschel, Peter Hülsmann and Volker Remmert. vii Contents 1 Erich Hückel’s Education and Scientific Awakening: The Path to Quantum Chemistry ...................... 1 1.1TheHückelFamily......................... 1 1.2 The First Years in Göttingen: Childhood, Elementary and Preparatory Schooling . .................. 4 1.3 Beginnings at the University of Göttingen and the War Years . 6 1.4 Continued Studies at Göttingen . .................. 8 1.5 Hückel’s Doctorate in Experimental Physics ............ 9 1.6 Excursion: First Collaboration with His Brother Walter . .... 14 1.7IntermediateStops......................... 15 1.7.1 David Hilbert’s Auxiliary Assistant ............. 15 1.7.2AssistanttoMaxBorn................... 18 1.8 Assistantship Under Peter Debye in Zurich and Habilitation Thesis on the Theory of Strong Electrolytes . .... 23 1.9 From the Theory of Strong Electrolytes to the Quantum Theory of Double Bonding . .................. 29 1.9.1 New Ambitions and Separation from Peter Debye . .... 29 1.9.2 Fellowship from the International Education Board in London with Frederick Donnan: New Research Orientation 33 1.9.3 Visit at Niels Bohr’s Institute in Copenhagen: The Beginnings of the Quantum Theory of Double Bonding 40 1.9.4 Fellowship from the Notgemeinschaft at the Leipzig Institute of Theoretical Physics . ........ 45 2 Erich Hückel’s Research Agenda During the 1930s: Underpinning Organic Chemistry with Quantum Theory ...... 49 2.1 The Quantum Theory of Double Bonding ............. 49 2.1.1Prehistory.......................... 49 2.1.2 The Beginnings of Hückel’s Quantum-Theoretical Interpretation of Double Bonding . ............. 54 2.1.3 Excursion: Hückel’s Physicochemical Experiments on the Stability of Cis and Trans Isomers . ........ 57 2.1.4 The Quantum-Mechanical Interpretation of Double Bonding 61 ix x Contents 2.1.5 The Response to Hückel’s Quantum Theory of Double Bonding ....................... 69 2.1.6 Lecturer of “Chemical Physics” in Stuttgart: 1930–1937 . 74 2.2 Quantum Theory of Aromaticity: Symmetry and Electronic Shell Completion . .................. 77 2.2.1 Prehistory and Hückel’s Point of Departure ........ 78 2.2.2 Quantum-Mechanical Interpretation of the Electronic Configuration of Benzene and Related Aromatic Compounds . .................. 81 2.2.3 Hückel’s Model of Benzene and Friedrich Hund’s LocalizationConditions................... 94 2.2.4 The Quantum-Theoretical Basis of the Chemical Behavior of Substituted Benzene Derivatives ........ 98 2.2.5 First Reactions to Hückel’s Papers on Aromatic Compounds 104 3 The Controversy Between Erich Hückel and Linus Pauling over the Benzene Problem ............. 115 3.1 Introduction: Calculating Perturbations with Spin Invariants and the Valence-Line Diagram in Chemistry . .... 117 3.2 The First Critical Exchanges . .................. 127 3.3 “Special Portion of Energy” Versus “Resonance Energy” . .... 133 4 Linus Pauling’s Breakthrough to the Theory of Aromatic Compounds and Hückel’s Reaction .................. 141 4.1 Introduction . ............................ 141 4.2 Avowal of the Molecular Orbital Method . ............. 143 4.3 A New Concept for Describing Aromaticity ............ 145 5 Hückel’s Efforts to Disseminate His Theory and Its Reception ... 151 6 Hückel’s Professional Career in National Socialist Germany .... 161 6.1 Membership in the National Socialist Welfare and German WorkersParty............................ 162 6.2 Extraordinary Professorship in Theoretical Physics at Marburg . 164 7 The Postwar Years ............................ 171 8 Summary and Concluding Remarks .................. 175 Appendix ................................... 179 Bibliography ................................. 181 Index ..................................... 195 Introduction Emerging disciplines in the border zone between physics and chemistry have attracted the attention of historians of science particularly in the last 20 years.1 Quantum chemistry,2 as an offshoot of theoretical chemistry, has recently acquired some importance in the history of chemistry.3 It is the product of close 1Cf. Hiebert, E.: Discipline Identification in Chemistry and Physics, in: Science in Context, 9(2) (1996), 93–119; Nye, M. J.: Physics and Chemistry: Commensurate or Incommensurate Sciences? in: The Invention of Physical Science, Intersections of Mathematics, Theology and Natural Philosophy since the Seventeenth Century – Essays in Honor of Erwin N. Hiebert. Kluwer Academic Publishers, Dordrecht 1992; From Chemical Philosophy to Theoretical Chemistry: Dynamics of Matter and Dynamics of Disciplines, 1800–1950. University of California Press, Berkeley 1994; Servos, J. W.: Physical Chemistry from Ostwald to Pauling, the Making of a Science in America. Princeton University Press, New Jersey 1990; Chemical Sciences in the 20th Century: Bridging Boundaries, edited by Carsten Reinhard. Wiley-VCH, Weinheim 2001 (incl. a comprehensive bibliography). 2In an earlier article I point out that the term “quantum chemistry” [Quantenchemie] first appeared in 1929. To my knowledge it was coined by the physicist Arthur Haas. Talks he had deliv- ered before the Viennese Chemico-Physical Society in the spring of 1929 are assembled in his book: Die Grundlagen der Quantenchemie: Eine Einleitung in vier Vorträge. It was published by the Akademische Verlagsgesellschaft in Leipzig. See Karachalios, A: Die Entstehung und Entwicklung der Quantenchemie in Deutschland, in: Mitteilungen der Gesellschaft Deutscher Chemiker Fachgruppe Geschichte der Chemie, 13 (1997), 163–179, footnote 2. 3Cf. Gavroglu, K. and Simões, A.: The Americans, the Germans and the Beginnings of Quantum Chemistry: The Confluence of Diverging Traditions, in: Historical Studies in the Physical and Biological Sciences, 25 (1994), 47–110; One Face or Many? The Role of Textbooks in Building the New Discipline of Quantum Chemistry,in:Communicating Chemistry. Textbooks and Their Audiences, 1789–1939, edited by Lundgren, A. and Bensaude-Vincent, Bernadette. Science History Publications, USA 2000, 415–449; Simões, A.: Converging Trajectories, Diverging Traditions: Chemical Bond, Valence, Quantum Mechanics and Chemistry, 1927–1937,Ph.D. Thesis, University of Maryland, College Park, 1993; Simões, A. and Gavroglu, K.: Different Legacies and Common Aims: Robert Mulliken, Linus Pauling and the Origins of Quantum Chemistry,in:Conceptual Perspectives in Quantum Chemistry, edited by Calais, J. L. and Kryachko, E. S. Kluwer Academic Publishers, Dordrecht 1997; Quantum Chemistry in Great Britain: Developing a Mathematical Framework for Quantum Chemistry, in: Studies in the History and Philosophy of Modern Physics, 31B (2000), 511–548; Issues in the History of Theoretical and Quantum Chemistry, 1927–1960,in:Chemical Sciences in the 20th Century: Bridging Boundaries, edited by Carsten Reinhardt. Wiley-VCH, Weinheim 2001, 51–74; Simões, xi xii Introduction interaction between chemistry, quantum physics and mathematics. Quantum chem- istry applies the approximative procedures used in quantum mechanics to chemical problems, with chemistry being its main foundation. Its interdisciplinary character derives from physical bases that are remolded to suit issues in chemistry.4 The meth- ods, theories and concepts used in quantum chemistry characteristically transgress the boundaries between chemistry and quantum physics. This cross-cultural rela- tionship is also reflected in the home fields of the scientists involved. It is primarily due to quantum physics that a reorientation of scientific inquiry to quantum- chemical issues emerged. Quantum physicists innovatively
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