Recent Experimental and Computational Advancesin Molecular Spectroscopy

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Recent Experimental andComputational Advancesin Molecular Spectroscopy

edited by

R. FaustoDepartment of Chemistry,University of Coimbra,Coimbra, Portugal

SPRINGER-SCIENCE+BUSINESS MEDIA, av.

Proceedings of the NATO Advanced Study Institute onMolecular Spectroscopy: Recent Experimental and Computational AdvancesPonta Delgada, Săo Miguel (Ayores), PortugalAugust 30 - September 11, 1992

A C.I.P. Catalogue record for this book is available from the Library of Congress

ISBN 978-94-010-4871-2 ISBN 978-94-011-1974-0 (eBook)

Printed an acid-tree paper

AII Rights Reserved© 1993 Springer Science+Business Media OordrechtOriginally published by Kluwer Academic Publishers in1993Softcover reprint of the hardcover 1st edition 1993No part of the material protected by this copyright notice may be reproduced orutilized in any form or by any means, electronic or mechanical, including photo­copying, recording or by any information storage and retrieval system, without writtenpermission from the copyright owner.

DOI 10.1007/978-94-011-1974-0

CONTENTS

Preface Organizing Committees List of Participants

Protonation of simple unsaturated organic compounds in their electronic ground and low lying excited states I. G. Csizmadia

Application of the CI-singles method in predicting the energy, propertie and

vii IX

XI

reactivity of molecules in their excited states 11 1. B. Foresman and H. B. Schlegel

Molecular sructure from rotational and vibrational transitions in electronic spectra 27 1. M. Hollas

From qualitative to quantitative analyses of circular dichroism spectra using the convex constraint algorithm 63 A. Perczel

Potential energy surfaces and vibrational anharmonicity 79 I. M. Mills

Development of an ab initio based database of vibrational force fields for organic molecules 99 P. Pulay, X. Zhou and G. Fogarasi

Computer-aided methods for the resolution enhancement of spectral data with special emphasis on infrared spectra 113 H. H. Mantsch and D . 1 . Moffatt

Raman spectroscopy: a survey on selected topics 125 1. J. C. Teixeira-Dias

a.~unsaturated carboxylic esters and their hydrogen bond complexes with substituted phenols: vibrational spectra-structure correlations 131 J. J. C. Teixeira-Dias and R. Fausto

Solvent effect on vibrational frequencies of substituted acetaldehydes 135 T. Varnali, V. Aviyente, B. Terryn and M. F. Ruiz-Lopez

Experimental and ab initio quantum mechanical studies of the vibrational spectra of isolated pyrimidine bases 141 W. B. Person, K. Szczepaniak, M. Szczesniak and 1. E. Del Bene

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vi

Pressure-tuning vibrational spectroscopy: applications from basic molecular spectroscopy to human cancer research 171 P. T. T. Wong

Vibrational spectroscopy of polyconjugated materials with electrical and non linear optical properties 191 G. Zerbi

Surface molecular spectroscopy 207 A. M . Bradshaw

Neutron molecular spectroscopy 229 J. Tomkinson

Recent advances in gas electron diffraction and structural studies by join quantum mechanical and experimental procedures 251 L. Schafer and J. D. Ewbank

Principles of multidimensional high-resolution NMR 257 D . L. Turner

NMR structural techniques in biochemical and bioinorganic systems: paramagnetic shift and relaxation probes 279 C. F. G. C. Geraldes

The physics of an atom in a molecule 313 R. F. W. Bader

Frontier orbital theory and chemical reactivity: the utility of spectroscopy and molecular orbital calculations 351 C. Ogretir and N. Kani~kall

Semiempirical molecular orbital theory: facts, myths and legends 369 T. Clark

The consistent force field: development of potential energy functions for conformational analysis 381 Kj. Rasmussen, S. B. Engelsell, 1. Fabricius and B. Rasmussen

Experimental and computational projects on molecular spectroscopy 421 S. Engelsen, 1. Fabricius, M. Peterson, P J A. Ribeiro-Claro and B.i. Whitaker

Short contributions: titles and authors 431 Author index 435 Subject index 437

PREFACE

This volume contains the lectures presented at the NATO Advanced study Institute (ASI) on "Molecular Spectroscopy: recent experimental and computational advances", held in the Hotel Ar;ores Atllintico, Ponta Delgada (Ar;ores), Portugal, from 30th August to 11 th September 1992.

The meeting aimed at gathering some of the most prestigious world experts in the fields of experimental and theoretical molecular spectroscopies, to give the participants the unique opportunity of sharing expertises in those active areas of research.

The scientific programme of the meeting integrated lectures on a large variety of topics (such as molecular dynamics and reactivity, conformational analysis, hydrogen bonding and solvent effects, spectroscopy of excited states, complex spectra interpretation and simulation, software development and biochemical applications of molecular spectroscopy) covering a wide range of molecular spectroscopic techniques either from an experimental or from a theoretical perspective. In addition, the scientific programme of the meeting also included two round tables focusing fundamental topics in molecular spectroscopy and tutorial classes. In the tutorial classes, the participants were directly involved in practical computational or laboratorial projects with different levels of difficulty. To this end, a sophisticated computer centre - integrating 3 main computers linked both locally and to the international network of computers, several PC's and a high level uv-visible spectrometer, making a total of 25 simultaneous workdesks - was installed at the Hotel where the meeting took place. The most up-t<>--<latc versions of computer programs useful in the fields of molecular spectroscopy, quantum chemistry and molecular mechanics (e.g ., GAUSSIAN 92, MOPAC 6.0, PROAIM, AVS, CHIMISTE, CFF, VAMP) were also made available to participants during the whole duration of the course.

Significant progress in the last few years deserved much attention in the Conference. In particular, advances in experimental teChniques were considered to result from new types of apparatus and from new ranges of experimental data covered, but also from the progressively much more important interplay between these techniques and the computational methods. Indeed, by providing new and more accurate data, some of the recent experimental advances provided also the stimulus for progress in the theoretical field, as was stressed in several communications in this meeting. On the other hand, it was also shown, in a very convincing way, that nowadays computational chemistry applied to spectroscopy can be quite competitive with experimental methods for reasonably complex molecules. and a great help in designing and planning the experiments.

The central idea behind this meeting can be traced three years ago. Since then until the last day of the ASI, many people were involved in this project. In particular. I wish to thank to all my colleagues in both the international and local committees. Professors Imre Csizmadia, John Hollas, Henry Mantsch, Willis Person, Jose Teixeira-Dias, Maria Leonor Duarte, Maria Leonor Medeiros and Dr. Francisco Gil, by their constant help and support.

vii

viii

The necessary financial support came mainly from the Scientific Committee of NATO and from the Directorate for Science of the Commision of the European Community (DG XII). In addition. various portuguese institutions. namely the Instituto Nacional de Investiga~l1o Cientffica (INIC). Junta Nacional de Investiga~l1o Cientffica e Tecnol6gica (JNICf) and Funda~iio Luso­Americana para 0 Desenvolvimento (FLAD) also gave lesser but nonetheless quite relevant financial contributions to the organization of this ASI. Other institutions provide valuable logistic support or contributed to the social programme of the meeting. Among those. I should mention the University of A~res. the Rectory of the University of Coimbra. the Regional Government of the A~ores. British Council. Portugal-UK Travel Fund. the City Councils of Coimbra and Ponta Delgada. Izasa Portugal -Distribui~oes T~cnicas. Banco Comercial dos A~ores. Banco Pinto e Sotto Mayor. Instituto de Investimento e Privatiza~oes dos A~ores (IIPA). the Tourism Office of Ponta Delgada. TAP-Air Portugal and Solu~Oes do Futuro.

I am particularly indebted to both CONVEX Supercomputer Portugal and Companhia IBM Portuguesa. as well as to the Computer Centre of the University of A~ores. which made available to this Institute very sophisticated and up-to-dated computational equipment and provided the technical assistance during the whole duration of the ASI. Part of this equipment was transported to the A~ores in a special aircraft kindly provided by the Defense Ministry of Portugal and the Portuguese Air Force. to whom I wish also to express my gratitude. To Prof. Lues F. Requixa Ferreira. my sincere thanks by his precious help to solve an important logistic problem that appeared just at the last moment before the meeting.

I would like also to thank to all the young students who made a very exceptional work at the secretariat during the busy days of the ASI - Ana Medeiros. Joana Duarte. Carla and Magui -. or during its preparation - Gabriela Martins and. in particular. my brother Jorge Louren~o. who retyped a very large number of abstracts to the book of abstracts of the meeting at the same time he was having his course final examinations at the University. A very special word of gratitude to Prof. Maria Leonor Medeiros and Francisco Gil by their outstanding dedication to the organization of this meeting. and to Prof. Jos~ Teixeira-Dias for his advice and for being always available.

Finally. I am also much indebted to all the personnel of Hotel A~ores AWintico and Agllncia A~oreana de Viagens for the professional quality of their work and service, and their constant kindness with all the participants. both of these essential ingredients to the success of the ASI.

Among the scientists who assembled and met in Ponta Delgada for thirteen days and now contribute to this book, there are some of the most qualified and prestigious world experts in the field. I can only hope that this book will record faithfully the scientific richness of the meeting. Indeed. I also wish that it can also serve to remember all those who have the opportunity of attending to this meeting. thirteen days of very rich human experiences. Certainly. the most valuable ones!

R. Fausto

ORGANIZING COMMITTEES

International Organizing Committee:

R. Fausto

I. G. Csizmadia

J. M. Hollas

H. H. Mantsch

W. B. Person

J. J. C. Teixeira-Dias

Local Committee:

R. Fausto

M. Leonor T.S. Duarte

F. P. S. C. Gil

M. Leonor P.S. Medeiros

J. J. C. Teixeira-Dias

University of Coimbra, Portugal (Director)

University of Toronto, Canada

University of Reading, UK

N.R.C.C. Winnipeg, Canada

University of Florida - Gainesville, USA

University of Coimbra, Portugal

University of Coimbra

Classical University of Lisboa

University of Coimbra

University of A~ores - Ponta Delgada

University of Coimbra

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LIST OF PARTICIPANTS

A. CAMILO P. ALVES Department of Chemistry University ofCoimbra 3049 Coimbra PORTUGAL

A. M. BRADSHAW Fritz-Haber Institute Max Planck Gesellschaft Fadarayweg 4-6 1000 Berlin 33 GERMANY

A. MARGARIDA AMADO Department of Chemistry University of Coimbra 3049 Coimbra PORTUGAL

ADNAN TAYMAZ Faculty of Sciences and Arts Akdeniz University P.O. Box 750 Antalya TURKEY

AIDA MOREIRA SILVA Department of Chemistry University ofCoimbra 3049 Coimbra PORTUGAL

ALEXANDER BAGATUR'YANTS Institute of Chemical Physics Academy of Sciences of Russia Kosygina Street 4 117977 Moscow RUSSIA

ALEXANDER ~ BORRO Department of Chemistry University of Reading Whiteknights Reading RG6 2AD ENGLAND - U.K.

xi

ALEXANDER MAKAROV Institute of Molecular Biology Academy of Sciences of Russia Vavilova Street 32 117984 Moscow RUSSIA

ALIST AIR P. RENDELL S .E.R.C. Daresbury Laboratory Theory and Computational Science Warrington WA44AD ENGLAND - U.K.

ANA URBANO Department of Biochemistry University of Coimbra 3049 Coimbra PORTUGAL

ANDRAs PERCZEL Department of Biochemistry Brandeis University Waltham MA02254 U.S.A.

ARBERT-JOSE DlANOUX Institute Max von Laue - Paul Langevin 156 X 38042 Grenoble Cedex FRANCE

BENJAMIN J. WHITAKER School of Chemistry University of Leeds Leeds LS2 9fT ENGLAND - U.K.

BRIGIT RASMUSSEN Department of Chemistry A Building 207 The Tecnhical University of Denmark 2800 Lyngby DENMARK

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CARLOS F.G.C. GERALDES Department of Biochemistry University ofCoimbra 3049 Coimbra PORTUGAL

CARLOS PENA-GARA Y Department of Physical Chemistry University of Valencia Doctor Moliner 50 46100 Burjassot SPAIN

CEMIL OGRETIR Department of Chemistry Faculty of Arts & Sciences Anadolu University 26470 Eskisehir TURKEY

CHRISTOPHER G. HICKMAN Department of Chemistry University of Southampton Southampton S09 5NH ENGLAND - U.K.

DAVID L. TURNER Department of Chemistry University of Southampton Southampton S095NH ENGLAND - U.K.

ELISHEV A GOLDSTEIN Department of Chemistry California State Polytechnic University Pomona - California 91768 U.S.A.

ELIZABETE C. LIMA D.C.T.D. University of A~'Ores 9500 Ponta Delgada PORTUGAL

FATMA SEVIN Department of Chemistry Hacettepe University 06532 Beytepe Ankara TURKEY

FERNANDA LADEIRO DUARTE L.N.E.T.l. Dep. of Technology ofChem.lndustries Estrada das Palmeiras 2745 Queluz de Baixo - Lisbon PORTUGAL

FERNANDO R. ORNELLAS Institute of Chemistry University of Sao Paulo 05508 Sao Paulo BRASIL

FRANCISCO P.S.C. GIL Department of Physics University of Coimbra 3049 Coimbra PORTUGAL

GEOFFREY M.J. WEST Computing Deptartment University of Staffordshire Mellor Building - College Road Stoke on Trent - Staffordshire ST4 2DE ENGLAND - U.K.

GIUSEPPE ZERBI Dep.ofChemistry and Chemical Eng. Giulio Natta - Poly tech. of Milan Piazza Leonardo da Vinci 32 20133 Milano ITALY

GUNTRAM RAUHUT Institute of Organic Chemistry I University of Erlangen-Nurnberg Henkestrasse 42 - 8520 Erlangen GERMANY

H. BERNHARD SCHLEGEL Department of Chemistry Wayne State University Detroit - Michigan 48202 U.S.A.

HALINA ABRAMCZYK Institute of Applied Radiation Chemistry Techical University Wroblewskiego 15 - 93-590 Lodz POLAND

HENRY H. MANTSCH Institute/or Biodiagnostics National Research Councilo/Canada Ellice A venue 435 Winnipeg R3B lY6 - Manitoba CANADA

IAN M. MILLS Department o/Chemistry University 0/ Reading Whiteknights - Reading RG6 2AD ENGLAND - U.K.

IMRE G. CSIZMADIA Department o/Chemistry University o/Toronto Toronto M5S I Al - Ontario CANADA

J. D. RINALDI Fac. 0/ Sci.- Lab. o/Theoretical Chem. Domaine Scientifique Victor Grignard University 0/ Nancy I B.P. 239 -54506 Vandoeuvre-les-Nancy FRANCE

J. MICHAEL HOLLAS Department a/Chemistry University 0/ Reading Whiteknights - Reading RG6 2AD ENGLAND - U.K.

JAN FLORIAN Institute 0/ Physics Charles University KE Karlovu -121 16 Prague CZECHOSLOVAKIA

JASMINA SABOLOVIC Institute/or Med. Res. & Occup. Health Ksaverska C2 41001 Zagreb CROATIA

JASPER FABRICIUS Department o/Chemistry A Building 207 The Tecnhical University 0/ Denmark 2800 Lyngby DENMARK

JEREMY G. FREY Department o/Chemistry University 0/ Southampton Southampton S09 5NH ENGLAND - U.K.

JOAO B.M. NOVO Institute o/Chemistry UNICAMP University o/Campinas Campinas 13081 - Sao Paulo BRASIL

JOHN TOMKINSON Rutherford Appleton Laboratory ISIS Facility - SERC Chilton - DIDCOT Oxon OXl1 OQX ENGLAND - U.K.

JORGE DE MEDEIROS D .C.T.D. University 0/ A~ores 9500 Ponta Delgada PORTUGAL

JOSE G.R. TOSTES Institute 0/ Chemistry Federal University Fluminense Rio de Janeiro BRASIL

JOSE J.C. TEIXEIRA-DIAS Department o/Chemistry University o/Coimbra 3049 Coimbra PORTUGAL

KJELD RASMUSSEN Department of Chemistry A Building 207

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The Tecnhical University of Denmark 2800 Lyngby DENMARK

KRYSTYNA S.-PERSON Department 0/ Chemistry University 0/ Florida Gainesville Florida 32611-2046 U.S.A.

xiv

LIGIA FRUNZA Insti.of Physi. & Technology of Materials P.O. Box MG 07 76900 Bucharest-Magurele ROMANIA

LOTHAR SCHAFER Department of Chemistry University of Arkansas Fayetteville - Arkansas 72701 U.S.A ..

Luis A.E. B. DE CARVALHO Department of Chemistry University ofCoimbra 3049 Coimbra PORTUGAL

Luis SERRANO-ANDRES Department of Physical Chemistry University of Valencia Doctor Moliner 50 46100 Burjassot SPAIN

M. ARMINDA PEDROSA Department of Chemistry University ofCoimbra 3049 Coimbra PORTUGAL

M. CRISTINA S. FERREIRA L.N.E .T.1 . Dep. of Technology of Chem.lndustries Estrada das Palmeiras 2745 Queluz de Baixo - Lisbon PORTUGAL

M. LEONOR P. DE MEDEIROS D.C.T.D. University of A~ores 9500 Ponta De/gada PORTUGAL

M. LEONOR T.S. DUARTE Department of Chemistry Classical University of Lisbon R. Ernesto Vasconcelos, Ed. Cl Campo Grande - 1700 Lisboa PORTUGAL

M. PAULA M. MARQUES Department of Biochemistry University ofCoimbra 3049 Coimbra PORTUGAL

MARCIA M.C. FERREIRA Institute of Chemistry UN1CAMP University of Camp in as Campinas 13081 - Sao Paulo BRASIL

M. RES AT APAK Department of Chemistry Faculty of Engineering University of Instambul Avci/ar 34850 Istanbul TURKEY

MARIO A. GAT A D.C.T.D . University of A~ores 9500 Ponta Delgada PORTUGAL

MARIO T. ROSADO Department of Chemistry Classical University of Lisbon R. Ernesto Vasconcelos , Ed. C 1 Campo Grande - 1700 Lisboa PORTUGAL

MARIA DO CARMO BARRETO D.C.T D . University of the A~ores 9500 Ponta Delgada PORTUGAL

MARIA ESTELA JARDIM Department ofChemisfly Classical University of Lisbon R. Ernesto Vasconcelos, Ed. C1 Campo Grande - 1700 Lisboa PORTUGAL

MARIA F.A.R. MOlT A Department of Chemistry Classical University of Lisbon R. Ernesto Vasconcelos, Ed. C1 Campo Grande - 1700 Lisboa PORTUGAL

MARK M. LAW Department of Chemistry University of Aberdeen Meston Walk - Old Aberdee AB9 2UE SCOTLAND - U.K.

MICHAEL GLUKHOVTSEV Institute of Organic Chemistry I University of Erlangen-Nurnberg Henkestrasse 42 - 8520 Erlangen GERMANY

MICKEL LOOS Fac. of Sci.- Lab. of Theoretical Chem. Domaine Scientifique Victor Grignard University of Nancy I B.P. 239 - 54506 Vandoeuvre-les-Nancy FRANCE

MIKE R. PETERSON Department of Chemistry University of Toronto Toronto M5S lAI - Ontario CANADA

MOZART N. RAMOS Dep.of Fundamental Chemistry Federal University of Pernambuco 50739 Recife - Pernambuco BRASIL

NEVIN KANISKAN Department of Chemistry Faculty of Arts & Sciences Anadolu University 26470 Eskisehir TURKEY

NICHOLAS G. FULTON Department of Physics and Astronomy University College London Gower Street - London WC 1 E 6BT England - U.K.

PATRICK T.T. WONG Institute for Biodiagnostics National Research Council of Canada Ellice A venue 435 Winnipeg R3B lY6 - Manitoba CANADA

PAUL V.R. SCHLEYER Institute of Organic Chemistry I University of Erlangen-Nurnberg Henkestrasse 42 - 8520 Erlangen GERMANY

PAULO J. A. RIBEIRO·CLARO Department of Chemistry University of Coimbra 3049 Coimbra PORTUGAL

PERICLES AKRIVOS Department of Gen. & Inorg.Chemistry Aristotle University ofThessaloniki P.O. Box 135 54006 Thessaloniki GREECE

PETER PULAY

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Department ofChemisOy & Biochemistry J.w. Fulbright Call. of Arts and Sciences University of Arkansas-115 Chem. Build. Fayetteville, Arkansas 72701 U.S.A.

RICHARD F.W. BADER Department of Chemistry McMaster University 1280 Main Street West Hamilton L8S 4M 1 - Ontario CANADA

ROY E. BRUNS Institute of Chemistry UNICAMP - University of Camp in as Campinas 13081 - Sao Paulo BRASIL

RUI FAUSTO Department of Chemistry University of Coimbra 3049 Coimbra PORTUGAL

SERGIO E. GALEMBECK Department of Fundamental Chemistry Federal University of Pernambuco 50739 Recife - Pernambuco BRASIL

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SOREN ENGELSEN Department of Chemistry A Building 207 The Tecnhical University of Denmark 2800 Lyngby DENMARK

SOTORIS XANTHEAS Pacific Northwest Laboratory Battele Blvd. P.O.Box 999 Richland, WA 99352 U.S.A.

SPYROS SPYROU National Hellenic Research Fundation Vassileos Constantinou Avenue 48 11635 Athens GREECE

STEFAN STOYANOV Department of Chemistry University of Sofia A. Ivanov Av. 1 - Sofia 1126 BULGARIA

SV A VA O. JONSDOTTIR Department of Chemistry A Building 207 The Tecnhical University of Denmark 2800 Lyngby DENMARK

TERESA M. TEIXEIRA-DIAS Department of Physics University of Coimbra 3049 Coimbra PORTUGAL

TEREZA V ARNALl Department of Chemistry Bogazici University F.E.F. Kimya P.K.2 - Bebek 80815 Istanbul TURKEY

TIMOTHY CLARK Institute of Organic Chemistry I University of Erlangen-Nurnberg Henkestrasse 42 - 8520 Erlangen GERMANY

VLADIMIR LOBACHOV Institute of Molecular Biology Academy of Sciences of Russia Vavilova Street 32 117984 Moscow RUSSIA

WAYNE E. SINCLAIR Department of Chemistry Imperial College London South Kensington London SW7 2A Y ENGLAND - U.K.

WILLIS B. PERSON Department of Chemistry University of Florida Gainesville, Florida 32611-2046 U.S.A.

WLADIA VIVIANI Fac. ofSci.- Lab. of Theoretical Chem . Domaille Scientifique Victor Grignard University of Nancy 1 B.P. 239 - 54506 Vandoeuvre-Ies-Nancy FRANCE

YVES G. SMEYERS Inst.de la Estructura de la Materia - CSIC Calle Serrano 123 Madrid SPAIN

YVONNE D. WEST Department of Chemistry University of Southampton Southampton S095NH ENGLAND - U.K.