ASPECTS OF CHEMICAL EVOLUTION XVllth SOLVAY CONFERENCE ON CHEMISTRY A D V A N C E S IN C H E M I C A L P H Y S I C S VOLUME LV EDITORIAL BOARD C. J. BALLHAUSEKNo,b enhaven Universitets Fysisk-Kemiske Institut. Kemisk Laboratorium IV, Kobenhaven, Denmark J. J. M. BEENAKKERRij,k suniversiteit te Leiden, Kamerlingh Onnes Laboratory, Leiden, Netherlands RICHARBD. BERNSTEINO,c cidental Research Corporation, Irvine, California, U.S.A. H. HAKENI,n stitut fur Theoretische und Angewandte Physik der Technischen Hochschule, Stuttgart, Germany Yu L. KLIMONTOVITMCoHs,c ow State University, Moscow, USSR RYOGOK uso, Department of Physics, University of Tokyo, Tokyo, Japan M. MANDELC, hemie-Complex der Rijks-Universiteit, Wassenaarseweg, Leiden, Netherlands PETERM AZURI,n stitute Lorentz voor Theoretische Natuurkunde, Nieuwsteeg, Leiden, Netherlands GREGOIRNEI COLISP, ool de Physique, Facult6 de Sciences, Universite Libre de Bruxelles, Bruxelles, Belgium S. ONO,I nstitute of Physics, University of Tokyo (College of General Education), Tokyo, Japan MICHAEPLH ILPOTTIB, M Research Center, San Jose, California, U.S.A. J. C. POLANYDI,e partment of Chemistry, University of Toronto, Toronto, On- tario, Canada YVESP OMEAUC,o mmissariat a I’Energie Atomique, Centre d’Etudes nucleares de Saclay, Division de la Physique, Gif-sur-Yvette, France B. PULLMAINn,s titut de Biologie, Physico-Chimique, Universite de Paris, Paris, France C. C. J. ROOTHAADNe, partments of Physics and Chemistry, The University of Chicago, Chicago, Illinois, U.S.A. IANR oss, Department of Chemistry, Australian National University, Canberra, Australia JOHNR oss, Department of Chemistry, Massachusetts Institute of Technology. Cambridge, Massachusetts, U .S .A. R. SCHECTEDRe, partment of Chemical Engineering, University of Texas at Aus- tin, Austin, Texas, U.S.A. I. SHAVITTD,e partment of Chemistry, Ohio State University, Columbus, Ohio, U.S.A. JANS TECKIIn, stitute of Physical Chemistry of the Polish Academy of Sciences, Warsaw, Poland GEORGSEZ ASZG, eneral Electric Corporate R & D, Zurich, Switzerland KAZUHITSAO MITAD,e partment of Physics, Faculty of Science, Kyoto University, Kyoto, Japan M. V. VOLKENSTEIInNs,t itute of Molecular Biology, Academy of Science, Mos- cow, USSR E. BRIGHWT ILSOND, epartment of Chemistry, Harvard University, Cambridge, Massachusetts, U.S.A. ASPECTS OF CHEMICAL EVOLUTION XVIIth SOLVAY CONFERENCE ON CHEMISTRY WASHINGTON, D.C., APRIL 23-APRIL 24, 1980 Edited by G. NICOLIS University of Brussels . Brussels. Belgium ADVANCES IN CHEMICAL PHYSICS VOLUME LV Series editors Ilya Prigogine Stuart A. Rice University sf Brussels Department of Chemistry Brussels. Belgium and and The James Franck Institute University of Texas University of Chicago Austin. Texas Chicago, Illinois AN INTERSCIENCE@P UBLICATION JOHN WILEY & SONS New York . Chichester . Brisbane . Toronto . Singapore An Interscience" Publication Copyright 0 1984 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging in Publication Data: Solvay Conference on Chemistry (17th : 1980 : Wash- ington, D.C.) Aspects of chemical evolution : XVlIth Solvay Conference on Chemistry, Washington, D.C., April 23- April 24, 1980. (Advances in chemical physics ; v. 55) "An Interscience publication." Includes index. I. Chemical evolution-Congresses. 2. Instituts Solvay-History-Congresses. 1. Nicolis, G., 1939- . 11. Title. 111. Series. QD453.A27 VOI. 55 [QH325] 541s 15771 83-12386 ISBN 0-471-88405-7 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 INTRODUCTION Few of us can any longer keep up with the flood of scientific literature, even in specialized subfields. Any attempt to do more, and be broadly educated with respect to a large domain of science, has the appearance of tilting at windmills. Yet the synthesis of ideas drawn from different subjects into new, powerful, general concepts is as valuable as ever, and the desire to remain educated persists in all scientists. This series, Ad- vunces in Chemical Physics, is devoted to helping the reader obtain gen- eral information about a wide variety of topics in chemical physics, which field we interpret very broadly. Our intent is to have experts present comprehensive analyses of subjects of interest and to encourage the expression of individual points of view. We hope that this approach to the presentation of an overview of a subject will both stimulate new re- search and serve as a personalized learning text for beginners in a field. ILYAP RIGOGINE STUARAT. RICE V PREFACE The reports and discussions contained in this volume have been pre- sented at the XVIIth Solvay conference on Chemistry. This was a special Solvay Conference organized jointly by the Solvay Institutes and the Na- tional Academy of Sciences of the United States, on the occasion of the 150th anniversary of the establishment of Belgium as an independent state. It was held in Washington, D.C., on April 23-24, 1980. The first part of the Conference was devoted to the historical role of the Solvay Institutes, and in particular of the Solvay Conferences on Physics and Chemistry, in promoting international scientific cooperation. The second part was devoted to some aspects of chemical evolution. This subject comprises an impressive number of different, yet complementary, questions having an interest in their own right. At the molecular level, it is believed that atmospheric conditions pre- vailing on earth some 4 billion years ago triggered an evolution of simple molecules to more complex forms. Eventually this led to biopolymer for- mation, which is at the basis of the origin of life. Somewhere along this path transition points such as chirality and self-replication arose, which conferred on evolution a markedly irreversible character. At the macroscopic level, evolution brought a drastic change in the environment. For instance, the earth’s atmosphere after the appearance of life is completely different than before. In addition, at this level, the analysis of physical, chemical, and biological problems shows that the evolution to complexity is accompanied by the successive breaking of symmetries of various kinds induced by two elements that continuously recur throughout the different stages: nonequilibrium constraints, nec- essary to enable the system to pump the appropriate raw materials from its environment; and nonlinearities in the form of feedbacks, necessary to speed up what would be otherwise an exceedingly slow rate of evo- lution. Finally, at the crucial moment of choice of a particular pathway among the multitude available, fluctuations play a crucial role. We hope that by bringing together presentations referring to all these different facets of evolution, the present volume will contribute to the development of an interdisciplinary approach to this fascinating field. The late Philip Handler, president of the U.S. Academy of Sciences, played a key role in the success of the Conference. Thanks are also due to Professor Bryce Crawford, Home Secretary of the Academy, and his vii viii PREFACE staff for the efficient handling of the various problems posed by the or- ganization of the meeting. ILY PRIGOG~NE A GREGOIRNE ICOLE Brussels, Belgium July 1983 Administrative Council of the Instituts Internationaux de Physique et de Chimie founded by E. Solvay President SOLVAPYre,s ident de la Commission Administrative des Instituts Internationaux de Physique et de Chimie Vice-president F. BINGENO,n dervoorzitter van de Raad van Beheer van de In- ternationale Instituten voor Fysica en Chemie Director I. PRIGOGINDEi,r ecteur des Instituts Internationaux de Physique et de Chimie Vice-Director J. PHILIPPOAT,d junct-Directeur van de Raad van Beheer van de Internationale Instituten voor Fysica en Chemie Treasurer J. REiGNIER, Penningmeester van de Raad van Beheer van de Internationale Instituten voor Fysica en Chemie Secretary G. NICOLISS,e cretaire du Conseil d’Administration des Instituts Internationaux de Physique et de Chimie Members R. DEBEVER P. GLANSDORFF A. JAUMOTTE A. MOLITOR G.V ANB INST Scientific Committee in Chemistry of the Instituts Internationaux de Physique et de Chimie founded by E. Solvay A. R. UBBELOHDIEm, perial College, Department of Chemical Engineering and Chemical Technology, London, England S. CLAESSONU, ppsala Universitet, Fysikalisk-Kemiska Institutionen, Uppsala, Sweden M. EIGENM, ax-Planck-Institut fur Biophysikalische Chemie, Nikolausberg, Got- tingen, Federal Republic of Germany B. HESS,M ax-Planck-Institut fur Ernahrungsphysiologie, Dortmund, Federal Re- public of Germany E. KATCHALSKTYh,e Weizmann Institute of Science, Department of Biophysics, Rehovot, Israel H. NORMANUT,n iversitC de Paris VI, Laboratoire de Synthkse Organique, Paris, France ix X SCIENTIFIC COMMITTEE IN CHEMISTRY W. LIPSCOMBH,a rvard University, Department of Chemistry, Cambridge, Mas- sachusetts, U.S.A. R. MARTINU, niversitt Libre de Bruxelles, Service de Chimie Organique, Brux- elles, Belgium J. E. MAYERU, niversity of California, San Diego, Department of Chemistry, Revelle College, La Jolla, California, U.S.A. Yu. OVCHINIKOSVhe, myakin Institute of Bioorganic Chemistry U.S.S.R. Acad- emy of Sciences, Moscow, U.S.S.R. L. PAULINGL,i nus Pauling Institute of Science and Medicine, Menlo Park, Cal- ifornia, U.S.A. V. PRELOGE,i dgenossische Laboratorium fur Organische Chernie, Zurich, Switz- erland LORDT ODDC, hrist’s College, Cambridge, England G. WITTIG,O rganisch-Chemisches Institiit der Universitat, Heidelberg, Federal Republic of Germany Participants E. AMALDII,s tituto di Fisica “Guglielmo Marconi,” Universita degli Studi. Piazzale delle Scienze, Rome, Italy G. AUCHMUTIYnd, iana University, Department of Mathematics, Bloomington, Indiana, U.S.A. A. BABLOYANTUZni,v ersitC Libre de Bruxelles, Service de Chimie Physique 11, Bruxelles, Belgium J. BELEWV, ice-president, Baylor University, Waco, Texas, U.S.A. A. BELLEMANUSn,i versitt Libre de Bruxelles, Campus Plaine, Bruxelles, Belgium A. BERGER, Institut d’astronomie et de GCophysique, Universite Catholique de Louvain, Louvain-La-Neuve, Belgium J. BIGELEISEANs,s embly Chairman, National Research Council, Assembly of Mathematical and Physical Sciences, State University of New York at Stony Brook, Stony Brook, New York, U.S.A. F. BINGENF,a culteit van Wetenschappen, Vrije Universiteit Brussel, Brussel, Belgium R. M. BOCK, The Graduate School, University of Wisconsin, Madison, Wisconsin, U.S.A. S. CLAESSONU,p psala Universitet, Fysikalisk-Kemiska Institutionen, Uppsala, Sweden M. DOLE,B aylor University, Department of Chemistry, Waco, Texas, U.S.A. M. EIGEN,M ax-Planck-Institut fur Biophysikalische Chemie, Nikolausberg, Gottingen, Federal Republic of Germany T. Enwax, Universite Libre de Bruxelles, Service de Chimie Physique 11, PARTICIPANTS xi Bruxelles, Belgium, and Northwestern University, Department of Applied Mathematics, Evanston, Illinois, U.S.A. P. FIFE, University of Arizona, Department of Mathematics, Tucson, Arizona, U.S.A. G. FONKEVNi,c e-president for Research, The University of Texas, Austin, Texas, U.S.A. H. FRISCHS, tate University of New York, Department of Chemistry, Albany, New York, U.S.A. M. GHIL,N ew York University, Courant Institute of Mathematical Sciences, New York, New York, U.S.A. P. GLANSDORFFU, niversite Libre de Bruxelles, Campus Plaine, Bruxelles, Belgium A. GOLDBETERU,n iversite Libre de Bruxelles, Service de Chemie Physique 11, Bruxelles, Belgium T. A. GRIFFYT, he University of Texas, Department of Physics, Austin, Texas, U.S.A. T. Guo, I.I.T., Research Institute, Annapolis, Maryland, U.S.A. W. Guo, I.I.T., Research Institute, Annapolis, Maryland, U.S.A. B. L. HAO, Chinese Academy of Sciences, Institute of Theoretical Physics, Beijing, People's Republic of China H. HERS,U niversite Catholique de Louvain, Faculte de Medecine, Laboratoire de Chimie Physiologique, Bruxelles, Belgium B. HESS, Max-Planck-Institut fur Ernahrungsphysiologie, Dortmund, Federal Republic of Germany J. HIERNAUXU,n iversite Libre de Bruxelles. Service de Chimie Physique 11, Bruxelles, Belgium H. D. HOLLANDH,a rvard University, Cambridge, Massachusetts, U.S.A. E. IMMERGUSTc,i entific American, New York, New York, U.S.A. K. KALTHOFFT,h e University of Texas at Austin, Department of Zoology, Austin, Texas, U.S.A. L. D. KAPLANN, ational Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Maryland, U.S.A. E. KATCHALSKTYh,e Weizmann Institute of Science, Rehovot, Israel S. KAUFFMANU,n iversity of Pennsylvania, Department of Biology, Philadelphia, Pennsylvania, U.S.A. D. KONDEPUDCI,e nter for Studies in Statistical Mechanics, The University of Texas, Austin, Texas P. LASZLOI,n stitut de Chimie, Universite de Liege, Liege, Belgium R. LEFEVERU, niversite Libre de Bruxelles, Service de Chimie Physique 11, Bruxelles, Belgium E. MARGOLIASHN,o rthwestern University, Department of Biochemistry and Molecular Biology, Evanston, Illinois, U.S.A.