Theoretical and Computational Models for Organic 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 B Physics

Plenum Publishing Corporation London and New York

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

NATO-PCO-DATA BASE

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-DATA BASE is possible in two ways:

- via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, I-00044 Frascati, Italy.

- via CD-ROM "NATO-PCO-DATA 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-PCO, Overijse, Belgium.

Series C: Mathematical and Physical Sciences - Vol. 339

Theoretical and Computational Models for Organic Chemistry edited by

Sebastiäo J. Formosinho Department of Chemistry, University of Coimbra, Coimbra, Portugal

Imre G. Csizmadia 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

Theoretica l and computationa l models fo r organi c chemistr y / edite d by Sebastii o J . Formosinho, Imr e G. Csizmadia, and Lui s G. Arnaut .

p. cm. — (NATO ASI ser ies . Serie s C, Mathematical and physica l science s ; vo l . 339)

Proceedings o f th e NATO Advanced Stud y Institut e on Theoretica l and Computational Models fo r Organi c Chemistry , Prai a de Port o Novo, Portugal . Aug. 26-Sept . 8 , 1990.

"Publishe d i n cooperatio n wit h NATO Sc ien t i f i c Affair s Division. " Include s index . ISBN 978-94-010-5589-5 ISBN 978-94-011-3584-9 (eBook)

1. Chemistry , Organic—Dat a processing—Congresses. 2 . Chemistry , Organic—Mathematical models—Congresses. I . Formosinho. Sebastii o J . , 1943- . I I . Csizmadia , I . G. I I I . Arnaut . Lui s G. , 1960-IV. NATO Advanced Stud y Institut e on Theoretica l and Computational Models fo r Organi c Chemistr y (199 0 : Prai a do Port o Novo, Portugal ) V. Series : NATO ASI ser ies . Serie s C, Mathematical and physica l science s

; no. 339.

QD255.5.E4T48 1991 547

1

.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.

DOI 10.1007/978-94-011-3584-9

Table of Contents

Preface Organizing Committee List of Lecturers List of Tutors List of Participants

I. G. Csizmadia Chemistry as an exact science

H. Bernhard Schlegel and Michael J. Frisch Computational bottlenecks in molecular orbital calculations

Bruce C. Garrett and Carl F. Melius Variational transition state theory calcillations of concerted hydrogen

vii viii Vlll

x xi

1

5

atom tunneling in water clusters and formaldehyde / water clusters 35

Antonio J. C. Varandas and Alberto A. C. C. Pais Double many-body expansion potential energy surface for 04(3 A), dynamics of the 0(3p) + 03(lAl) reaction, and second virial coefficients of molecular oxygen 55

Jean-Louis Rivail, Daniel Rinaldi and M. F. Ruiz-Lopez The self-consistent reaction field model for molecular computations in solution

79

Paul G. Mezey New symmetry theorems and similarity rules for transition structures 93

Gustavo A. Arteca and Paul G. Mezey A topological analysis of macromolecular folding patterns 111

N. L. Allinger Molecular mechanics 125

Gerald M. Maggiora, S. L. Narasimhan, C. A. Granatir, J. R. Blinn and J. B. Moon Predicting the three-dimensional structure of proteins by homology-based model building 137

Sebastiao J. Formosinho Understanding chemical reactivity through the intersecting-state model 159

vi

Josef Michl The states of an electron pair and photochemical reactivity 207

Michael A. Robb and F. Bernardi Ab-initio modelling of chemical reactivity using MC-SCF and VB methods

253

Fernando Bernardi, Massimo Olivucci and Michael A. Robb The supra-supra mechanism of forbidden and allowed cycloaddition reactions: an analysis a VB model 289

NoamAgmon Excited state proton transfer reactions

C. Ogretir and N. Kaniskan An exploratory study to correlate experimental and theoretical acidities of organic molecules

Cleanthes A. Nicolaides and Petros Valtazanos Molecules with "volcanic" ground hypersurfaces. Structure, stability

315

335

and energetics 355

Feliu Maseras, Miquel Duran, Agusti Lledos and Juan Bertran Molecular hydrogen as a ligand in transition metal complexes 375

M. 1. Calhorda Molecular orbital studies of reductive elimination reactions 397

G. A. Arteca, A. Bottoni, M. Duran, R. Fausto, M. R. Peterson, H. D. Thomas Laboratory projects in computational organic chemistry 411

Subject index 429

PREFACE

The papers in this volume were presented at the NATO Advanced Study Institute held in Porto Novo, Portugal, August 26 - September 8, 1990. The Institute has been able to cover a wide spectrum of the Theoretical and Computational Models for organic molecules and organic reactions, ranging from the ab initio to the more empirical approaches, in the tradition established in the previous Institutes at S. Feliu de Guixols (Spain) and Altinoluk (Turkey). The continuity with this work was achieved by inviting half of the lecturers present in those meetings. But other important subjects were also covered at Porto Novo by new lecturers, both from universities and the industry. Molecular Mechanics, Protein Structure and Unidimensional Models were introduced by the first time. The concept of building on the expertise already acquired and available, both in terms of methods and contents, to develop in new directions, was appreciated by participants and lecturers.

The Institute first considered the fundamentals of molecular orbital computations and ab initio methods and the construction of Potential Energy Surfaces. These subjects were further explored in several applications related with optimization of equilibrium geometries and transition structures. Practical examples were studied in Tutorial sessions and solved in the computational projects making use of the Gaussian 88 and Gaussian 90 programs.

Empirical models can be complementary to the quantum-mechanical ones in equilibrium geometry optimizations. Thus, the Institute also devoted a considerable amount of time to the presentation of the basis and recent developments of Molecular Mechanics, also explored through computational projects with the MM2 program, and to topological and "template empirical methods" for the design of the protein structures.

Subsequently, the problems of reactivity in small molecules were approached via the "Variational Transition State Theory" and Dynamical Studies. The POLYRA TE program was available to the computational laboratory users. To deal with reactivity in larger molecules, both in ground and excited states, or to find trends of reactivity in families of reactions, simpler models have to be employed. A representative sample of such simple methods was presented, ranging from the quantum mechanical Valence Bond Diabatic Methods of Evans, to state correlation diagrams, and to classical models based on the intersection of potential energy curves. Structures-reactivity relationships were also discussed. Emphasis was given to the role of solvent on chemical reactivity and to the dynamical processes occurring in a very short time scale.

This course was centered in the use of computational tools. The participants had direct and unlimited access to a Convex-120 machine with 16 terminals, to 2 clustered VAX Stations with 4 terminals, one IBM PS 2 and Macintoshes. Adequate service was provided both by the tutors and by Convex and Digital personnel. 28 groups opened accounts for the Convex; they used a total of 182 CPU hours and requested a total memory of 6.02xl()6 KBytes. The VAX stations were used virtually 100% during operation time.

We would like to express our gratitute to the NATO Science Division and to JNICT for the award of grants which enabled the meeting to be held, and to CONVEX and DIGITAL for their outstanding support to the computational laboratory.

vii

Organizing Committee

Prof. SJ. Formosinho (Director) Departamento de Quimica Universidade de Coimbra 3049 Coimbra Codex Ponugal

Prof. N. L. Allinger Department of Chemistry University of Georgia Athens, Georgia 30602 United States

Prof. I. G. Csizmadia Department of Chemistry University of Toronto 80 St. George St. Toronto, Ontario M5S 1A1 Canada

Dr. L. G. Arnaut (Co-director) Departamento de Quimica Universidade de Coimbra 3049 Coimbra Codex Portugal

List of Lecturers

Prof. N. Agmon

Prof. N. L. Allinger

Prof. F. Bernardi

Prof. J. Bertran

Department of Physical Chemistry The Hebrew University Jerusalem 91904 Israel

Department of Chemistry University of Georgia Athens, Georgia 30602 United States

Dipartimento di Chimica "G. Ciamician" Univ. di Bologna Via Selmi 240126 Bologna Italy

Dipartament de Quimica Universitat Autonoma de Barcelona 08193 Bellaterra (Barcelona) Spain

viii

Prof. MJ. Calhorda

Prof. I. G. Csizmadia

Prof. S.l Formosinho

Dr. B. C. Garrett

Dr. M. R. Lopez

Dr. G. M. Maggiora

Prof. P.G. Mezey

Prof. J. Michl

Prof. C. Nicolaides

Centro de Qufmica Estrutural Instituto Superior Tecnico 1096 Lisboa Codex Portugal

Department of Chemistry University of Toronto 80 St. George St. Toronto, Ontario M5S 1A1 Canada

Departamento de Quimica Universidade de Coimbra 3049 Coimbra Codex Portugal

Molecular Science Research Center Battelle Pacific Northwest Laboratory Battelle Boulevard Richland, Washington 99352 United States

Laboratoire de Chimie Theorique Universite de Nancy I B.P.239 54506 Vandoeuvre-Les- Nancy Cedex France

Director of Computational Chemistry The Upjohn Company Kalamazoo, Michigan 49001 United States

Department of Chemistry and Chemical Engineering University of Saskatchewan Saskatoon S7N ONO Canada

Center for Structure and Reactivity Department of Chemistry University of Texas at Austin Austin, Tx. 78712-1167 United States

Theoretical Physical Chemistry Institute National Hellenic Research Foundation 48, Vassileos Constantinou Av. Athens 116-35 Greece

ix

x

Prof. e. Ogretir

Prof. M.A Robb

Prof. H.B. Schlegel

Prof. AJ.e. Varandas

List of Tutors

Dr. Gustavo Arteca

Dr. A Bottoni

Dr. M. Duran

Dr. R. Fausto

Dr. Mike Peterson

Chemistry Department Anadolu University 26470 Eskisehir Turkey Department of Chemistry King's College London, Strand, London WC2R 2LS United Kingdom

Department of Chemistry Wayne State University Detroit, Michigan 48202 United States

Departamento de Qufmica Universidade de Coimbra 3049 Coimbra Codex Portugal

Department of Chemistry Univ. of Saskatchewan Saskatoon, Saskatchewan S7N OWO Canada

Dipartimento di Chimica Univ. di Bologna Via Selmi, 2 40126 Bologna Italy

Dep. de Qufmica Fac. de Ciencies Univ. Autonoma de Barcelona 08193 Bellaterra Spain

Departamento de Qufmica Universidade de Coimbra 3000 Coimbra Portugal

Department of Chemistry Univ. of Saskatchewan Saskatoon, Saskatchewan S7N OWO Canada

Dr. Henry Thomas

List of Participants

Mr. David Amarilio

Dr. Victorya A viyente

Dr. Alessandro Bagno

Prof. Nurettin Balcioglu

Dr. Laura Bonati

Mr. L. Batista Carvalho

Dr. A. Pereiras Castro

Department of Chemistry University of Georgia Athens, Georgia 30602 United States

N.C.R. "Democritos" GR-1531O, Ag. Paraskevi Athens P.O. Box 60228 Greece

Chemistry Department Bosphorous University 80815 Bebek Istambul Turkey

CNR, Meccanismi Reazioni Organiche Via Marzolo 1 1-35131 Padova Italy

Department of Chemistry Beytepe Campus Hacettepe University Ankara Turkey

Dip. di Chimica Fisica e Elettrochimica Univ. di Milano Via Golgi 19 20133 Milan Italy

Departamento de Qufmica Universidade de Coimbra 3000 Coimbra Portugal

Dep. de Quimica Fisica Fac. Quimica Univ. Santiago 15706 Santiago de Compostela Spain

xi

xii

Prof. Emine Cebe

Prof. Mustafa Cebe

Dr. Paulo Ribeiro Claro

Mr. U go Cosentino

Mrs. M. Ceu Costa

Dr. Giinay Demirel

Ms. Ozden Ozel Evin

Mr. Adelino Galvao

Dr. Elisheva Goldstein

Dr. Giiliimser Giindogan

Physics Department Faculty of Sciedce Uludag University Bursa Turkey

Chemistry Department Uludag University Bursa Turkey

Departamento de Qufmica Universidade de Coimbra 3000 Coimbra Portugal

Dip. di Chimica Fisica e Elettrochimica Univ. di Milano, Via Golgi 19 20133 Milan Italy

DTIQ,LNETI Estrada das Palmeiras 2745 Queluz Portugal

Department of Chemistry Middle East Technical University 06531 Ankara Turkey

Department of Chemistry Middle East Technical University 06531 Ankara Turkey

Centro de Qufmica Estrutural Instituto Superior Tecnico 1096 Lisboa Codex Portugal

Chemistry California State Polytechic Univ. 3801 West Temple Av, Pomona CA 91768-4032 United States

Middle East Tecnical University Department of Chemistry 06531 Ankara Turkey

Dr. Vera Kolb

Mr. Andreas Koster

Mr. Michel Loos

Mr. J.-F. Marcoccia

Ms. M. J. Seixas Melo

Dr. Javier Modrego

Dr. Giorgio Moro

Mr. George Mousdis

Mr. J. J. Soares Neto

Department of Chemistry University of Wisconsin-Parks ide Kenosha, WI 53141 United States

Theoretische Chemie University of Hannover Am Kleinen Felde 30 3000 Hannover 1 Germany

Laboratoire de Chimie Theorique Univ. de Nancy I 54506 Vandoeuvre-Les-Nancy Cedex France

Dep. of Chemistry Univ. of Toronto 80 St. George St. Toronto, Ontario M5S 1A1 Canada

Centro de Tecnologia Qufmica e Biologica R. Quinta Grande, 6 27800eiras Portugal

Inorganic Chemistry Laboratory Univ. of Oxford South Parks Rd. Oxford, OX1 3QR United Kingdom

Dip. di Chimica Fisica e Elettrochimica Univ. di Milano Via Golgi 19 20133 Milan Italy

National Hellenic Research Foundation 48 Vassileos Constantinou Ave. Athens 11635 Greece

Department of Chemistry Aarhus University DK 8000 Aarhus C Denmark

xiii

xiv

Dr. Massimo Olivucci

Mr. A. Canelas Pais

Mr. Ian Palmer

Ms. Ana Paula Paiva

Prof. N. B. Peynircioglu

Mr. Joey Pierce

Dr. Fernando Pina

Mr. Ioannis Ragazos

Dr. M. Mar Reguero

Ms. M. I. M. Rodriguez

Department of Chemistry King's College London Strand London WC2R 2LS United Kingdom

Departamento de Quimica Universidade de Coirnbra 3000 Coirnbra Portugal

Department of Chemistry King's College London Strand London WC2R 2LS United Kingdom

Departamento de Quimica Universidade de Lisboa R. E. Vasconcelos, Ed. Cl, 5Q pi so 1700 Lisboa Portugal

Department of Chemistry Middle East Technical University 06531 Ankara Turkey

Department of Chemistry University of Texas at Austin Austin Tx 78712 United States

Fac. Ciencias e Tecnologia Univ. Nova de Lisboa, Qta. Torre 2825 Monte da Caparica Portugal

Department of Chemistry King's College London Strand London WC2R 2LS United Kingdom

Department of Chemistry King's College London Strand London WC2R 2LS United Kingdom

Dep. de Quirnica Fisica y Analitica Univ. Oviedo, Julian Claveria sIn 33006 Oviedo Spain

xv

Dr. M. Amelia Santos C.Q.E., Instituto Superior Tecnico Av. Rovisco Pais 1096 Lisboa Codex Portugal

Dr. Zheng Shi Department of Chemistry Dalhousie Univ. Halifax, Nova Scotia B3H 4J3 Canada

Mr. Alan Smith Chemical Laboratory University of Kent at Canterbury KentCT2 7NH United Kingdom

Dr. Canan Unaleroglu Department of Chemistry Beytepe Campus Hacettepe University 06532 Ankara Turkey

Dr. G. Suzzi Valli Dipartimento de Chimica "Ciamician" Via Selmi 2 40126 Bologna Italy

Dr. Tereza Varnali Bogazi~i University F. E.F Kimya Bebek 80815 Istanbul Turkey

Dr. A. Venturini CNR, I. Co. C.E.A. Via della Chimica 8 40064 Ozzano Emilia (BO) Italy

Mr. Luis Veiros C.Q.E. Grupo II, Complexo I Instituto Superior Tecnico 1096 Lisboa Codex Portugal

Dr. L. Vazquez Vidal Dep. de Quimica Fisica, Fac. Quimica Univ. Santiago 15706 Santiago de Compostela Spain

Ms. Wladia Viviani Laboratoire de Chimie Theorique Univ. de Nancy I 54506 Vandoeuvre-Les-Nancy Cedex France