Vibrations at Surfaces Vibrations at Surfaces Edited by R.Caudano J.-M. Gilles and A. A. Lucas Facultes Universitaires Notre-Dame de la Paix Namur, Belgium PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging in Publication Data Main entry under title: Vibrations at Surfaces. "Proceedings of the Second International Conference on Vibrations at Surfaces, held September 10-12, 1980, at the Facultes Notre-Dame de la Paix, Namur, Belgium" - Verso of t.p. Bibliography: p. Includes index. 1. Vibrational spectra - Congresses. I. -Cauda no, R. II. Gilles, J.-M. III. Lucas, A. A. IV. International Conference on Vibrations at Surfaces (2nd: 1980 : Facultes universitaires Notre Dame de la Paix, Namur) V_ Facultes universitaires Notre-Dame de la Pa/x, Namur. QD96.V53V53 541.3'453 81-15830 ISBN-13: 978-1-46844060-7 e-ISBN-13: 978-1-4684-4058-4 ~ACR2 001: 10.10071978-1-4684-4058-4 Proceedings of the Second International Conference on Vibrations at Surfaces, held September 10-12, 1980, at the Facultes Notre-Dame de la Paix, Namur, Belgium © 1982 Plenum Press, New York Softcover reprint of the hardcover 1st edition 1982 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE This volume contains most of the invited and contributed papers presented at the second international conference devoted to the general topic "Vibrations at Surfaces" and which took place from 10 to 12 September 1980 at the Facu1tes Notre-Dame de 1a Paix in Namur, Belgium. The conference was organized to review the large amount of information gathered in this field over the late seventies as a result of th~ rapid improvements and dissemination of surface spectroscopic technique such a electron energy loss, infrared and Raman surface spectroscopies. Much time was devoted to Raman spectroscopy of adsorbed mo1e 'cu1es. After several years of vivid debate over the causes of the observed large enhancement of Raman cross section, a clearer pic ture emerges from the papers presented here: the actual value of the enhancement factor does depend in a complicated manner on long range surface roughness, atomic-scale roughness and the dielectric properties of the substrate as well as on the electronic structure of the molecule in its adsorbed state. Less controversial are the results obtained with electron energy loss spectroscopy (EELS) and several sessions of the con ference were devoted to the approach. As witnessed by the growing number of laboratories using the technique, EELS is now a mature spectroscopic tool for the characterization and analysis of the chemisorption bond. One of the ultimate goals of surface vibrational spectroscopies being a better understanding of the energy transfer and dissipation processes and of chemical reaction paths at solid surfaces, a few papers were included to deal in the advances in this area. Inelastic atomic and molecular beam scattering as a way to investigate surface vibrations was not developed in the conference except for one paper. At the writing of this preface, important v PREFACE new advances are being made with this technique which, in the next few years, may be expected to join force with photon and electron spectroscopies for the experimental studies of dynamical surface properties. We have great pleasure in acknowledging the enthusiastic re sponse and participation of our invited speakers and we thank all authors for their diligent preparation of the manuscripts. We are particularly indebted to Mr. J. Ghijsen, our Conference Secretary, for his outstanding job in meeting deadlines before and after the conference and in keeping people happy during the meeting. Much of the conference success is to be credited to him. We are grateful to our younger colleagues, Drs. Darville, Delrue, Pireaux, Riga and Mr. Thiry for their very valuable help with the practical organization of the meeting and the editing of the manuscripts. Nearly all of the papers were typed by Mme. Coulonval-Polet, whom we thank most sincerely for her usual efficiency and care. We are also thankful to Mr. Lotin of the Audio-Visual Center for taking care of the proper reproduction of the figures and tables in the manuscripts. The accommodation and social programs were organized by Mr. G. Kelner and his staff at the Public Relation Office with their customary superior style. Many thanks to them for their outstanding service. Finally we would like to express our deepest gratitude to all of our sponsors for providing the credit, financial and otherwise, which helped us ensure a participation at the highest level: Facult~s Notre-Dame de la Paix IBM Belgium and IBM Europe Belgian National Science Foundation (FNRS) Belgian Ministry for Science Policy State University of Mons Shell Esso Belgium Labofina ICI Belgian Physical Society European Physical Society R. Caudano J.M. Gilles A. Lucas CONTENTS 1. Clean and Adsorbed Surfaces Theory of phonons on clean and adsorbed surfaces. 1 L. Dobrzynski, B. Djafari-Rouhani (Invited) Desorption by resonant multiphoton excitation of internal adsorbate vibration 17 J. Heidberg, H. Stein, E. Riehl Face centered cubic transition metal surface vibrations ••....• 39 G. Allan, J. Lopez Atom motion at model crystal surfaces 57 J.E. Black Infrared reflection absorption and emission study of methyl alcohol adsorption on Mo03 films. 71 M. Ito Rotational accommodation at surfaces via Rayleigh phonons . • . . . . . • • • • • •• • .••. 79 B. Feuerbacher Arrangement of CO molecules adsorbed on low index metal surfaces : a comparison between LEED and HREELS or IRS . . • . • • • . . • • • . • . 91 J.P. Biberian, M.A. Van Hove Effects of many body forces on the adsorbate induced phonon structure •.•••••..••..... 105 G. Doyen Vibrational lifetimes for molecules adsorbed on metal surfaces. • • • • . • . • . . . . . . 113 M. Persson, B.N.J. Persson Surface modes of a spherical void at the proxi- mity of a surface • . . • • . . . . • . • • . . . • 123 A. Ronveaux, A. Magnus vii viii CONTENTS Theoretical study of the vibrational properties of a (117)F.C.C. surface. . . • • . • • .... 129 G. Armand, P. Masri (Abstract) The chemisorption of CO on Cu : an ab initio cluster model study . • . . . . . . . 131 P.S. Bagus, M. Seel (Abstract) Librational modes of molecules on metals. 133 H. Morawitz, T.R. Koehler (Abstract) Vibrations of neutrally adsorbed atoms on transition metal surfaces . . . . . . . . . . . . . . . . 135 C.M. Sayers (Abstract) 2. Electron energy loss spectroscopy EELS of surface phonons and vibrations of adsorbed spec ies. . . . . . . . • . . . . . . . . • . . 137 S. Lehwald, H. Ibach (Invited) Electronic surface resonance enhancement of vibra tional loss intensities.. .....•...•. 153 R.F. Willis (Invited) EELS of collective surface modes 169 S. Andersson (Invited) The adsorption and co-adsorption with. CO of NO on Cu (11 0) studied with ELS and LEED. ....... 187 J.F. Wendelken The adsorption of H20 on Ru(OOI) : chemisorption and hydrogen bonding . . . . .. .......... 201 P.A. Thiel, F.M. Hoffmann, W.H. Weinberg On the excitation mechanism of vibrational modes of C2H4 chemisorbed on Pt(lll) and Ni(lll) by EELS . . . .. .............. 215 A.M. Bare, S. Lehwald, H. Ibach Vibrations measured at metal surfaces by EELS : a review table.. .... ......... 231 P. Thiry High resolution electron spectroscopy : instru mentation and some results on a tungsten surface 249 A. Adnot (Invited - Abstract) Theory of electron energy loss spectroscopy. 251 M. Sunjic (Invited - Abstract) Adsorption sites of CO on the (III) face of Pt lONi90 single crystal alloy. . . . .. ........ 253 J.C. Bertolini, B. Tardy (Abstract) CONTENTS ix 3. Infrared Spectroscopy A comparison of the reflection-absorption infrared method with the electron energy loss method for studying vibrations at surfaces • • • • • . . • . . . • . . • . • • • . • . • • . 255 R.G. Greenler (Invited) Applications of IR ellipsometric spectroscopy to surface studies • . • • . • ...... 265 M.J. Dignam (Invited) Reflection-absorption infrared spectroscopy using a Fourier transform spectrometer : a study of carbon monoxide adsorbed on Pt(III) •••.••. 289 M.D. Baker, M.A. Chesters Collective vibrational modes in isotopic mix tures of CO adsorbed on Cu(IOO) ... 299 B.N.J. Persson, R. Ryberg Intrinsic line widths of CO adsorbed on Cu(IOO) .. 309 R. Ryberg "In situ" characterization of surface complexes of propene on oxidation catalysts (I.R. spectroscopy) .. 315 R. Delobel, M. Le Bras, M. Traisnel, J.M. Leroy Infra-red cryospectroscopic study on the interaction of CO with a (III)Ni- and NaCl-film at low temperature under ultrahigh vacuum . . • . . . . . • . • • . . . . . • 323 J. Reidberg, I. RussIa Infrared study of comparative adsorption of some alcohols and thiols on y-alumina . . • • • . • • 333 J. Travert, O. Saur, M. Benaissa, J. Lamotte, J .C. Lavalley Infrared spectra of species adsorbed on films or well-defined surfaces : a tabulation of the inves- tigated systems .••• 341 J. Darville 4. Surface Enhanced Raman Scattering Surface enhanced Raman scattering from character- ized metal surfaces. • • . • • • • • . • • • . • 361 J.C. Tsang, J.R. Kirtley, S.S. Jha (Invited) Enhanced Raman spectroscopy from adsorbates on silver : evidence for the "Adatom Model" • • • • • 379 A. Otto, I. Pockrand, J. Billmann (Invited) x CONTENTS High resolution electron energy loss and surface enhanced Raman studies of pyridine and benzene on Ag (III). . . . . . . . . . . . . . . . . . . . . . . . .391 J.E. Demuth, P.N. Sanda, J.M. Warlaumont, J.C. Tsang, K. Christmann (Invited) Raman spectroscopy of thin organic films by inte- grated optical techniques . . . . . . . . . . .... 413 J.D. Swalen, J.F. Rabolt Enhanced Raman scattering from molecules adsorbed at metal surfaces . . . . ..... 421 K. Arya, R. Zeyher Enhanced Raman scattering from molecules adsorbed on resonant metal particles ................4 31 C.G. Blatchford, J.A. Creighton Enhanced Raman scattering from molecules adsorbed on small nickel particles ................. 439 l.v. Krasser Surface enhanced Raman scattering from different types of metal substrates .................4 45 R. Dornhaus The relevance of spatial variation in the electro magnetic vector potential for surface Raman scat- tering. . . . . .. ..... ... 457 J.K. Sass, H. Neff, S. Holloway, M. Moskovits 5. Other Spectroscopies Adsorption of marked acetic acid on alumina studied by lETS ... . . . .. . ... .. 465 S. de Cheveigne, S. Gauthier, J. Klein, A. Leger The adsorption of unsaturated hydrocarbons on alumi nium oxide and magnesium oxide : an inelastic elec- tron tunnelling spectroscopy study. . . . . . ... 471 W.J. Nelson, D.G. Walmsley Vibrations in benzene and toluene monolayers on the basal plane of graphite . . . . . . . . . . . ... 483 R. Stockmeyer, M. Monkenbusch Photoacoustic and photothermal surface spectroscopy .... 499 S.D. Kanstad, P.E. Nordal (Abstract) CONTENTS xi 6. Surface Molecular Dynamics and Reactivity Energy transfer processes in gas and surface reactions. . . • . • . . . . . . . • . • • 501 B. Kasemo (Invited) Electron-hole pairs, molecular vibrations, and rate processes at metal surfaces . . • 519 J.W. Gadzuk, H. Metiu (Invited) Static and dynamic aspects. of chemisorption. 541 B.I. Lundqvist (Invited) Vibrational activation and surface reactivity; SF6 interaction with silicon induced by infra- red laser radiation •..••..••...•.•..... 573 T.J. Chuang Index ... . .•••..•.•.••••....• 579