Molecular Liquids: New Perspectives in Physics and Chemistry

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1989).

Series C: Mathematical and Physical Sciences - Vol. 379

Molecular Liquids: New Perspectives in Physics and Chemistry edited by

Jose J . C. Teixeira-Dias Departamento de Qui mica, Universidade de Coimbra, Coimbra, Portugal

WW Springer-Science+Business Media, B.V

Proceedings of the NATO Advanced Study Institute on Molecular Liquids: New Perspectives in Physics and Chemistry Luso, Portugal September 22 - October 3,1991

ISBN 978-94-010-5258-0 ISBN 978-94-011-2832-2 (eBook) DOI 10.1007/978-94-011-2832-2

Printed on acid-free paper

All Rights Reserved © 1992 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1992 Softcover reprint of the hardcover 1st edition 1992 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 photo­copying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

CONTENTS

~h~ ~

List of Participants xi

Radiation scattering experiments on fluids 1 P.A. EgelstaJf

Illustrations of radiation scattering data 29 P.A. EgelstaJf

Diffraction studies of spatial correlations in disordered molecular assemblies 45 I.C. Dore

Microscopic dynamics in simple liquids 77 U. Balucani

Smoluchowski-Vlasov equations, reference memory function approximation, and molecular models for transport and relaxation in fluids 95 HL. Friedman, F.O. Raineri, H. Resat

Basic theory of intermolecular forces 121 A.D. Buckingham

Conformational studies in organic liquids 147 I J.e. Teixeira-Dias, L.A.E. Batista de Carvalho, P.J.A. Ribeiro-Claro

Dynamical properties of simple molecular liquids 157 R. Vallauri

Thermodynamics of solutions, especially dilute solutions of nonelectrolytes 175 E. Wilhelm

Molecular dynanlics sinlulation of non-simple liquids 207 S. Toxvaerd

Time-, frequency- and polarization- resolved infrared spectroscopy of hydrogen-bonded systems 225 A. Laubereau, H. Graener

Computer simulation study of the bond-angle distributions and relative diffusion in liquids 239 M. Canales, I.A. Padro

Ion-ion interaction in a polarizable medium 253 C. larque, A.D. Buckingham

Experimental approach to the internal field problem 267 V.A. Zamkov

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Vibrational spectroscopic studies of intermolecular dynamics in organic liquids 275 f. Ymwood

Raman spectroscopic studies on the interaction and dynamics ofN,N-dimethylformamide in the liquid phase. The effect of isotopic dilution 307 VM. Shelley

Nuclear Magnetic Resonance (NMR) and Quasielastic Neutron Scattering (QNS) of molecular liquids 319 MD. Zeidler

Structure and properties of molten metal carboxylates 333 HD. Burrows

A comparative study of molecular correlation times of CSz/CC4 mixtures as observed by means of far infrared, Raman and Rayleigh spectroscopy 351 Th. Dorjmuller, F. Strehle, L. Potthast

Application of an equilibrium renewal process to inhomogeneous1y-broadened vibrational spectra of condensed phases 369 M. Perrot, f.-M. De Zen, W.G. Rothschild

Incoherent inelastic neutron scattering from molecular liquids. Study of semiclassical corrections 379 M. Diraison, G. Tarjus, S. Bratos, f-Cl. Leicknam

Dynamic cross correlations in molten salts and soft-sphere binary liquid mixtures. A molecular dynamics study. 393 I. Trullds, I.A. Padr6

High pressure study of collision induced light scattering in C02-Kr mixture 415 A. Hacura, K. Pasterny, F.G. Baglin

Second and third virial coefficients of collision-induced absorption and light scattering 423 M. Moraldi, L. Frommhold

The influence of relaxation processes in matrices on the spectroscopic properties of the solvated electron 447 H. Abramczyk, f. Kroh

Investigation of structure in liquids by the temperature dependence of depolarized light scattering 461 N.B. Rozhdestvenskaya, V.I. Rolich

Chemical kinetics and vibrational spectroscopy: An analysis of weak charge-transfer complexing reactions 469 M.Besnard

Structure of liquid cyclopropane M.l. Cabaco, M. Besnard, M.C. Bellissent-Funel, Y. Guissani, B. Guillot

Computer simulation of the vibrational spectrum of a system with ultrafast chemical reaction S. Weiss

Nonequilibrium molecular dynamics of classical fluids H.A. Posch, W.G. Hoover

MD simulation of depolarized Rayleigh and FIR spectra in binary liquid mixtures H. Stassen, U. Mittag, J. Samios

Short contributions: titles and authors

Author index

Subject index

vii

513

523

527

549

569

571

573

Preface

This volume contains the lectures presented at the NATO Advanced Study Institute (ASI) on "Molecular Liquids: new perspectives in Physics and Chemistry", held in the Hotel das Termas, Luso, Portugal, from 22nd September to 3rd October 1991.

Famous for its pure mineral water, undoubtely the most important molecular liquid on Earth, Luso spa is located 27 km north of Coimbra, west of Bw;aco forest mountain, 200 meters above sea level, and 25 km from the coast. Luso and the surrounding area is a peaceful place of luxuriant vegetation and natural beauty, well documented in the poster of this ASI. In this natural environment, the Hotel offered a quiet and relaxed atmosphere wonderfully suited for intellectual activity.

The main objective of this Institute was to survey progress in the area of Molecular Liquids, with particular emphasis on the Structure and Dynamics ofliquids and on the interplay of Inter- and Intramolecular Processes. True to its title, this school combined an advanced teaching standpoint with an emphasis on new perspectives and recent advances in the area of liquids formed by simple molecules. A wide range of topics was covered, in particular, in the areas of intermolecular forces, statistical mechanics, microscopic dynamics of simple liquids, thermodynamics of solutions, non-equilibrium molecular dynamics, molecular models for transport and relaxation in fluids, molecular dynamics simulations of liquids, statistical band shape theories of liquids, conformational studies, fast-exchange dynamics in donor-acceptor complexes, and hydrogen bonding. A large variety of experimental techniques was also considered, namely, neutron scattering, X-ray diffraction, infrared, Raman, and nuclear magnetic resonance spectroscopies, quasi elastic neutron scattering, high-precision time-resolved coherent Raman spectroscopy and EXAFS (Extended X-ray Absorption Fine Structure).

Significant progress in the last few years also deserved much attention in this ASI. In particular, advances in experimental techniques were considered to result either from new types of apparatus or from new ranges of experimental data covered. Progress in this area was partially ascribed to the availability of neutron spallation and of synchroton radiation sources, to the technical improvements in the area of high-precision time resolved coherent Raman spectroscopy, and to the advantages of EXAFS which provides a local probe and is suitable for ionic solutions. In the field of time-resolved spectroscopic techniques, a novel CARS spectrometer with 80 femtoseconds resolution and an improved measuring accuracy was described. By providing new and more accurate data, some of the recent experimental advances provided also the stimulus for progress in the theoretical field. In particular, a quantum-mechanical theory of high energy incoherent neutron scattering from liquid water was presented to interpret recent data obtained with spallation sources. Molecular dynamics simulation of quantum mechanical systems was also described. In particular, the path-integral Monte-Carlo method was described and applied to supercritical D2, solid and liquid H2, solid Ne and Ar. Application of non-equilibrium molecular dynamics to the evaluation of transport coefficients was also described and discussed.

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The central idea behind this meeting can be traced two years ago to the initiative and encouragement of the "European Molecular Liquids Group". I am most grateful to all my colleagues in the Organizing Committee, Professors James MacConnell, Thomas Dorfmul1er, Jack YalWood, John Dore, Renzo Vallauri, and Harald Posch, by their constant help and support. I am also most indebted to Prof. Harald Posch, Scientific Coordinator of EMLG until December 1990, with whom I kept an almost permanently open phone line to ask for help and advice, especially during the last few months before the meeting.

The necessary financial support came mainly from the Scientifc Committee of NATO and, to a lesser but nonetheless quite relevant extent, from various portuguese institutions, namely, the Instituto Nacional de Investiga<;iio Cientffica (INIC), Funda<;iio Calouste Gulbenkian, Funda<;iio Luso-Americana para 0 Desenvolvimento, Junta Nacional de Investiga~ao Cientffica e Tecnol6gica (JNICf). Other institutions provided valuable logistic support and among those I should mention the Rectory of the University of Coimbra, Funda<;iio Bissaya Barreto, the Archives of the University of Coimbra, the Tourisme Office in Luso, the City Council of Coimbra.

I wish to thank to all my colleagues and collaborators at the research group on Molecular Physical Chemistry, in Coimbra, namely, Ant6nio Amorim da Costa, Paulo Jorge Ribeiro-Claro, Rui Fausto, LUIS Alberto Batista de Carvalho, Maria Paula Marques, Francisco Campos Gil and Aida Moreira da Silva, for their help and advice in the organization of this meeting, and to Teresa, my wife, for planning and entirely organizing the social programme of the Institute. This included a reception and lunch at the Rectory, a visit to the University King John Library and St. Michael Chapel, a reception at the Town Hall, visits to the ruins and museum of the roman town Conimbriga, and to Bu<;aco and its luxuriant forest, a visit and lunch in wine cellars, a visit to Obidos and lunch in the Pousada, the recital in Coimbra, and the conference dinner with folk dancing and Coimbra's "fado" singing. I am particularly indebted to Miss Ana Margarida Amado (Guida) for the work at the secretariat which was assigned to her since the very beginning of the preparation of the ASI. As a student, she had to put aside many valuable hours of studying Biochemistry to work instead for this meeting. Various students rushed in to help the secretariat, especially during the very busy days of the ASI. I would like to mention and thank Teresa Freire (Tete), Sandra Nobre, Ana Alexandra Lemos (Xana), my son Filipe, Gabriela Martins (Gabi), and Cristina Marques. Finally, I am also much indebted to all the personnel of Hotel das Termas, 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 ASL

Among the scientists who assembled and met in Luso for twelve 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, for then I am certain that it will be a useful reference source for future work. In addition, I wish that the meeting in Luso, as an occasion of excellent science and informal gathering with a warm and relaxed atmosphere throughout the whole meeting, will be remembered and cherished for years to come by all the participants. As to the human experience, certainly the most valuable, it will remain forever engraved in the memories of those who, like me, had the unique and high privilege of gathering in Luso at that time.

Jose J.e. Teixeira-Dias

List of Participants

Director: .

Prof. lJ.C. Teixeira-Dias Departamento de Qufmica, Univ. Coimbra Portugal

Lecturers:

Prof. U. Balucani Inst. Elettronica Quantistica, Firenze Italia

Prof. M. Besnard Universite Bordeaux I, Talence France

Prof. S. Bratos Universite Pierre et Marie Curie, Paris France

Prof. A.D. Buckingham Univ. Chemical Laboratory, Cambridge United Kingdom

Prof. J.C. Dore University Department of Physics, Kent United Kingdom

Prof. Th. DorfmiiJler Univ. Fakultat fUr Chemie, Bielefeld Deutschland

Prof. P.A. Egelstaff Univ. Department of Physics, OntaIio Canada

Prof. H.L. Friedman University Department of Chemistry, New York USA

Prof. A. Laubereau Univ Physikalische Institut, Bayreuth Deutschland

xi

Prof. J.R. McConnell Institut for Advanced Studies, Dublin Ireland

Prof. H. Posch Universitat Physikal Institut, Wien Austria

Prof. lJ.C. Teixeira-Dias Departamento de Quimica, Univ. Coimbra Portugal

Prof. S. Toxvaerd H.C. Orsted Institutet, Kobenhavn Denmark

Prof. R. Vallauri Dipartimento di Fisica, Firenze ltalia

Prof. E. Wilhelm Institut Physikalische Chemie, Wien Austria

Prof. M. Zeidler Institut Physikalische Chemie, Aachen Deutschland

Prof. J. Yarwood Univ. Dept. of Chemistry, Durham United Kingdom

xii

Participants:

Dr H. Abramczyk Univ. Inst. App. Rad. Chern., L6dz Poland

Prof. A.C.P. Alves Departamento de Quimica, Univ. Coimbra Portugal

Prof. M. Alves Marques Centro Fisica da Materia Condensada, Lisboa Portugal

Mr. L. Amaral Centro Fisica da Materia Condensada, Lisboa Portugal

Prof. A.M. Amorim da Costa Departamento de Quimica, Univ. Coimbra Portugal

Mr. H. Azzouz Univsersite.Pierre et Marie Curie, Paris France

Prof. E. Barbosa Centro de Electroquimica e Cinetica, Lisboa Portugal

Mr. Luis A.E. Batista de Carvalho Departamento de Quimica, Univ. Coimbra Portugal

Mr. C. Borsdorf Univ. Fakultat Chemie, Bielefeld Deutschland

Prof. H. Burrows Departamento de Quimica, Univ. Coimbra Portugal

Prof. R.E. Bruns Inst. Quimica/ Univ. Est. Campinas, Silo Paulo Brasil

Dr. I. Caba\!o Lab. Spectrsc. Mol. et Cristalline, Talence France

Mr. Francisco P.S.C. Gil Departamento de Fisica, Univ. Coimbra Portugal

Dr. M. Canales Facultat d'Informatica (UPC), Barcelona Spain

Dr. D.C. Champeney School of Mathematics and Physics, Norwich United Kingdom

Dr. F. Cilloco Istituto di Struttura della Materia (CNR), Roma Italia

Dr. B. Cohen University Department of Chemistry, Beer Sheva Israel

Dr. J.-M. De Zen Universite Bordeaux I, Talence France

Mr. M. Diraison Univsersite Pierre et Marie Curie, Paris France

Mr. W.Egger Institut fiir Experimentalphysik, Wien Austria

Dr. R. Fausto Departamento de Quimica, Univ. Coimbra Portugal

Dr. J.L. Gomez-Estevez Univ Dept Fisica Fonamental, Barcelona Spain

Dr. D. Giilen University Physics Department, Ankara Turkey

Dr. A. Hacura Uniwersytet Instytut Fizyki, Katowice Poland

Miss T. Haliloglu Univ. Chemical Engineering Dept., Istanbul Turkey

Dr. E. Hawlicka Univ. Inst. App. Rad. Chern., L6dz Poland

Prof. M.E. Jardim Faculdade de Ciencias, Lisboa Portugal

Mr. R. Karawatzki Institut fUr Experimentalphysik, Wien Austria

Mr. C.L. Kneifel Univ. Chern. SUNY, Stony Brook, New York USA

Mr. S. V. Kuzmin Univ. Dep. Theor. Physics, Odessa

Dr. L. Letamendia Universite Bordeaux I, Talence France

Mr. R. Ludwig lust. Phys. Chemie RWTH, Aachen Deutschland

Dr. S. Magazu 1st. di Fisica Contrada Papardo, Messina Italia

Dr. D. Majolino 1st. di Fisica Contrada Papardo, Messina ltalia

MSc. M.P.M. Marques Departamento de Qufmica, Univ. Coimbra Portugal

Mr. J. Marti Univ. Dep. Ffsica Fonarnental, Barcelona Spain

Miss A.G.T. Martins Departamento de Qufmica, Univ. Coimbra Portugal

Dr. M. Moraldi Dip. Fisica Sezione I.N.F.N., Firenze ltalia

Dr. M. Neumann UniversitlU Physikal Institut, Wien Austria

Prof. C. Ogretir Anadolu Universitesi, Eskisehir Turkey

Dr. N. Papadopoulos University Dept.Chemistry, Thessaloniki Greece

Dr. K. Pastemy Universytet Slaski/lnstitut Fizyili, Katowice Poland

Prof. A. Pedrosa Departamento de Quimica, Univ. Coimbra Portugal

Prof. M C. Pedroso Lima Departamento de Qufmica, Univ. Coimbra Portugal

Dr. T. Podoski lust. Maths Phys. Chern., Gdynia Poland

Dr. PJ.A. Ribeiro-Claro Departamento de Qufmica, Univ. Coimbra Portugal

Prof. N. Rozhdestvenskaya Moika Quai 16, St.Petersburg

Dr. I.S. Scarmfnio

xiii

lust. Qufmica, Univ. Est. Campinas, Sao Paulo Brasil

Dr. V. Shelley University Chemical Department, Durham United Kingdom

Mr. H. Stassen Universitat Fakultat fijr Chemie, Bielefeld Deutschland

Dr. J. Trullas Facultat di Informatica (UPC), Barcelona Spain

C.J. Uribe University Chemical Department, Cambridge United Kingdom

Mr. M. Vencour Institut fiir Experimentalphysik, Wien Austria

Dr. B.A. Veytsman University Dep. of Theor. Physics, Odessa

Mr. S. Wappmann Universitat Institut fiir Biophysik, Regensburg Deutschland

Dr. S. Weiss University Chemical Department, Beer Sheva Israel

Prof. V. Zamkov Moika Quai 16, St.Petersburg

Mr. E. Zoidis Universitat Fakultat fiir Chemie, Bielefeld Deutschland

xv