Theoretical and Computational Models for Organic Chemistry PDF
Preview Theoretical and Computational Models for Organic Chemistry
Theoretical and Computational Models for Organci Chemistry NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical Kluwer Academic Publishers and Physical Sciences Dordrecht, Boston and London D Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change NATO-PCO-DAA TBASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DAAT BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DAAT BASE) hosted by ESRIN, Via Galileo Galilei, I-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DAAT BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PC,O Overijse, Belgium. Series C: Mathematical and Physical Sciences - Vol. 339 Theoretical and Computational Models for Organic Chemistry edited by Sebastiä o J. Formosinho Department of Chemistry, University of Coimbra, Coimbra, Portugal Imre G. Csizmadai Department of Chemistry, University of Toronto, Toronto, Canada and Luis G. Arnaut Department of Chemistry, University of Coimbra, Coimbra, Portugal Springer Science+Business Media, B.V. Proceedings of the NATO Advanced Study Institute on Theoretical and Computational Models for Organic Chemistry Praia de Porto Novo, Portugal August 26-September 8,1990 Library of Congress Cataloging-in-Publication Data Theoretical and computational models fo r organi c chemistr y / edite d by Sebastii o J. Formosinho, Imre G. Csizmadia, and Luis G. Arnaut. p. cm. — (NATO ASI series . Series C, Mathematical and physical sciences ; vol . 339) Proceedings of th eN ATO Advanced Study Institut e on Theoretica l and Computational Models fo r Organic Chemistry, Praia de Porto Novo, Portugal. Aug. 26-Sept. 8,1 990. "Published i nc ooperatio n wit h NATO Scientifi c Affair s Division. " Includes index. ISBN9 78-94-010-5589-5 ISBN9 78-94-011-3584-9 (eBook) DOI 10.1007/978-94-011-3584-9 1. Chemistry, Organic—Data processing—Congresses. 2. Chemistry, Organic—Mathematical models—Congresses. I . Formosinho. Sebastii o J., 1943- . II .C sizmadia, I . G. III .A rnaut. Luis G., 1960- IV. NATO Advanced Study Institut e on Theoretica l and Computational Modesl fo r Organic Chemistry (1990 : Prai a do Porto Novo, Portugal ) V. Series: NATO ASI series . Series C, Mathematical and physical sciences no. 339. ; QD255.5.E4T84 1991 5471.00285—dc20 91-18386 CIP ISBN 978-94-010-5589-5 Printed on acid-free paper All Rights Reserved © 1991 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1991 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo- copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. Table of Contents Preface vii OrganizingC ommittee viii List of Lecturers Vlll List of Tutors x List of Participants xi I. G. Csizmadia Chemistrya s an exacts cience 1 H. BernhardS chlegela nd Michael J. Frisch Computationabl ottlenecksin molecularo rbital calculations 5 Bruce C. Garrett and Carl F. Melius Variational transition statet heory calcillationso f concertedh ydrogen atom tunnelingi n water clustersa nd formaldehyde/ waterc lusters 35 Antonio J. C. Varandasa nd Alberto A. C. C. Pais Double many-bodye xpansionp otentiale nergys urfacef or 04(3A ), dynamicso f the 0(3p) + 03(lAl) reaction,a nd secondv irial coefficients of molecularo xygen 55 Jean-LouisR ivail, Daniel Rinaldi and M. F. Ruiz-Lopez The self-consistenrte actionf ield model for molecularc omputationsin solution 79 Paul G. Mezey New symmetryt heoremsa nd similarity rules for transition structures 93 GustavoA . Arteca and Paul G. Mezey A topological analysiso f macromoleculafro lding patterns 111 N. L. Allinger Molecular mechanics 125 Gerald M. Maggiora, S. L. NarasimhanC, . A. Granatir,J . R. Blinn and J. B. Moon Predictingt he three-dimensionasl tructureo f proteinsb y homology-based model building 137 SebastiaoJ . Formosinho Understandingc hemicalr eactivity through the intersecting-statme odel 159 vi JosefM ichl The stateso f an electronp air andp hotochemicarl eactivity 207 Michael A. Robb andF . Bernardi Ab-initio modelling of chemicalr eactivity using MC-SCF and VB methods 253 FernandoB ernardi,M assimoO livucci and Michael A. Robb The supra-supram echanismo f forbidden and allowedc ycloadditionr eactions: an analysisa VB model 289 NoamAgmon Excited statep roton transferr eactions 315 C. Ogretir and N. Kaniskan An exploratorys tudy to correlatee xperimentaal nd theoretical aciditieso f organicm olecules 335 CleanthesA . Nicolaidesa nd PetrosV altazanos Moleculesw ith "volcanic" groundh ypersurfaces. Structurest,a bility and energetics 355 Feliu Maseras,M iquel Duran, Agusti Lledos and JuanB ertran Molecular hydrogena s a ligand in transitionm etal complexes 375 M. 1. Calhorda Molecularo rbital studieso f reductivee liminationr eactions 397 G. A. Arteca, A. Bottoni, M. Duran, R. Fausto,M . R. Peterson,H . D. Thomas Laboratoryp rojectsi n computationaol rganicc hemistry 411 Subjecti ndex 429 PREFACE The papersi n this volume were presenteda t the NATO AdvancedS tudy Institute held in Porto Novo, Portugal,A ugust 26 -Septembe8r , 1990. The Institute has beena ble to cover a wide spectrumo f the Theoreticala nd ComputationalM odels for organic moleculesa nd organic reactions,r anging from the ab initio to the more empirical approachesi,n the tradition establishedin the previousI nstitutesa t S. Feliu de Guixols (Spain) and Altinoluk (Turkey). The continuity with this work was achievedb y inviting half of the lecturers presentin thosem eetings.B ut otheri mportants ubjectsw ere also covereda t Porto Novo by new lecturers, both from universitiesa nd the industry. Molecular Mechanics,P rotein Structurea nd UnidimensionalM odels were introducedb y the first time. The concepto f building on the expertisea lready acquireda nd available, both in terms of methodsa nd contents,t o developi n new directions,w as appreciatedb y participantsa nd lecturers. The Institute first consideredth e fundamentalso f molecularo rbital computationsa nd ab initio methodsa nd the constructiono f PotentialE nergy Surfaces.T heses ubjectsw ere further exploredi n severala pplicationsr elatedw ith optimizationo f equilibrium geometries and transition structures.P racticale xamplesw ere studiedi n Tutorial sessionsa nd solvedi n the computationapl rojectsm aking useo f the Gaussian8 8 and Gaussian9 0 programs. Empirical models can be complementaryt o the quantum-mechanicaol nes in equilibrium geometryo ptimizations.T hus, the Institute also devoteda considerablea mount of time to the presentationo f the basisa nd recentd evelopmentso f Molecular Mechanics, also exploredt hrough computationalp rojectsw ith the MM2 program,a nd to topological and "templatee mpirical methods"f or the designo f the protein structures. Subsequentlyt,h e problemso f reactivity in small moleculesw ere approachedv ia the "Variational Transition StateT heory" and Dynamical Studies.T he POLYRAT E program was available to the computationall aboratory users. To deal with reactivity in larger molecules,b oth in ground and excited states,o r to find trendso f reactivity in families of reactions,s impler modelsh ave to be employed.A representatives ampleo f such simple methodsw as presentedr, anging from the quantumm echanicalV alence Bond Diabatic Methods of Evans, to state correlation diagrams,a nd to classicalm odels basedo n the intersectiono f potential energy curves. Structures-reactivityr elationshipsw ere also discussed.E mphasisw as given to the role of solvent on chemicalr eactivity and to the dynamicalp rocesseso ccurringi n a very short time scale. This coursew as centeredi n the use of computationalt ools. The participantsh ad direct and unlimited accesst o a Convex-120m achinew ith 16 terminals, to 2 clustered VAX Stationsw ith 4 terminals,o ne IBM PS 2 and Macintoshes.A dequates ervicew as provided both by the tutors and by Convex and Digital personnel.2 8 groups opened accountsf or the Convex; they useda total of 182 CPU hours and requesteda total memory of 6.02xl()6 KBytes. The VAX stationsw ere usedv irtually 100% during operationt ime. We would like to expresso ur gratitute to the NATO ScienceD ivision and to JNICT for the award of grants which enabledt he meeting to be held, and to CONVEX and DIGITAL for their outstandings upportt o the computationalla boratory. vii Organizing Committee Prof. SJ.F ormosinho( Director) Departamentod e Quimica Universidaded e Coimbra 3049 CoimbraC odex Ponugal Prof. N. L. Allinger Departmenot f Chemistry University of Georgia Athens,G eorgia3 0602 United States Prof. I. G. Csizmadia Departmenot f Chemistry University of Toronto 80 St. GeorgeS t. Toronto, Ontario M5S 1A1 Canada Dr. L. G. Arnaut (Co-director) Departamentod e Quimica Universidaded e Coimbra 3049 CoimbraC odex Portugal List of Lecturers Prof. N. Agmon Departmenot f PhysicalC hemistry The HebrewU niversity Jerusalem9 1904 Israel Prof. N. L. Allinger Departmenot f Chemistry University of Georgia Athens,G eorgia3 0602 United States Prof. F. Bernardi Dipartimentod i Chimica "G. Ciamician" Univ. di Bologna Via Selmi 240126B ologna Italy Prof. J. Bertran Dipartamentd e Quimica UniversitatA utonomad e Barcelona 08193 Bellaterra( Barcelona) Spain viii ix Prof. MJ. Calhorda Centrod e QufmicaE strutural Instituto SuperiorT ecnico 1096L isboa Codex Portugal Prof. I. G. Csizmadia Departmenot f Chemistry University of Toronto 80 St. GeorgeS t. Toronto, Ontario M5S 1A1 Canada Prof. S.l Formosinho Departamentod e Quimica Universidaded e Coimbra 3049 CoimbraC odex Portugal Dr. B. C. Garrett Molecular ScienceR esearchC enter Battelle PacificN orthwestL aboratory Battelle Boulevard Richland, Washington9 9352 United States Dr. M. R. Lopez Laboratoired e Chimie Theorique Universited e Nancy I B.P.239 54506V andoeuvre-LesN-ancy Cedex France Dr. G. M. Maggiora Director of ComputationaCl hemistry The Upjohn Company Kalamazoo,M ichigan 49001 United States Prof. P.G. Mezey Departmenot f Chemistrya nd ChemicalE ngineering University of Saskatchewan SaskatoonS 7N ONO Canada Prof. J. Michl Centerf or Structurea nd Reactivity Departmenot f Chemistry University of Texasa t Austin Austin, Tx. 78712-1167 United States Prof. C. Nicolaides TheoreticalP hysicalC hemistryI nstitute National Hellenic ResearchF oundation 48, VassileosC onstantinouA v. Athens 116-35 Greece x e. Prof. Ogretir ChemistryD epartment Anadolu University 26470E skisehir Turkey Prof. M.A Robb Departmenot f Chemistry King's College London, Strand,L ondon WC2R 2LS United Kingdom Prof. H.B. Schlegel Departmenot f Chemistry WayneS tateU niversity Detroit, Michigan 48202 United States AJ.e. Prof. Varandas Departamentod e Qufmica Universidaded e Coimbra 3049 CoimbraC odex Portugal List of Tutors Dr. GustavoA rteca Departmenot f Chemistry Univ. of Saskatchewan SaskatoonS, askatchewaSn 7N OWO Canada Dr. A Bottoni Dipartimentod i Chimica Univ. di Bologna Via Selmi, 2 40126B ologna Italy Dr. M. Duran Dep. de Qufmica Fac. de Ciencies Univ. Autonomad e Barcelona 08193 Bellaterra Spain Dr. R. Fausto Departamentod e Qufmica Universidaded e Coimbra 3000 Coimbra Portugal Dr. Mike Peterson Departmenot f Chemistry Univ. of Saskatchewan SaskatoonS, askatchewaSn 7N OWO Canada
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