Table Of ContentCluster Models for
Surface and
Bulk Phenomena
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 New York and London
C Mathematical Kluwer Academic Publishers
and Physical Sciences Dordrecht, Boston, and London
D Behavioral 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
Recent Volumes in this Series
Volume 278-Painleve Transcendents
edited by D. Levi and P. Winternitz
Volume 279-Fundamental Aspects of Inert Gases in Solids
edited by S. E. Donnelly and J. H. Evans
Volume 280-Chaos, Order, and Patterns
edited by Roberto Artuso, Predrag Cvitanovic, and Giulio Casati
Volume 281-Low-Dimensional Structures in Semiconductors: From Basic
Physics to Applications
edited by A. R. Peaker and H. G. Grimmeiss
Volume 282-Quantum Measurements in Optics
edited by Paolo Tombesi and Daniel F. Walls
Volume 283-Cluster Models for Surface and Bulk Phenomena
edited by Gianfranco Pacchioni, Paul S. Bagus, and Fulvia Parmigiani
Volume 284-Asymptotics beyond All Orders
edited by Harvey Segur, Saleh Tanveer, and Hetbert Levine
Volume 285-Highlights in Condensed Matter Physics and Future Prospects
edited by Leo Esaki
Series B: Physics
Cluster Models for
Surface and
Bulk Phenomena
Edited by
Gianfranco Pacchioni
Universita di Milano
Milano, Italy
PaulS.8agus
IBM Research Division, Almaden Research Center
San Jose, California
and
Fulvio Parmigiani
Centro Informazioni Studi Esperienze (CISE)
Milano, Italy
Plenum Press
New York and London
Published in cooperation with NATO Scientific Affairs Division
Proceedings of a NATO Advanced Researc'h Workshop
on Cluster Models for Surface and Bulk Phenomena,
held April 19-26, 1991,
in Erice, Sicily, Italy
Library of Congress Cataloging-in-Publication Data
Cluster models for surface and bulk phenomena I ed'ted by Glanfranco
Pacch1onl. Paul S. Bagus, and Fulvia Parmiglanl.
p. em. -- (NATO ASI serIes. Series B, PhysIcs; v. 283)
"Published In cooperat,on with NATO Soientiflc Affa,rs D,v,s,on."
"Proceedings of a NATO Advanced Research Workshop on Cluster
Models for Surface and Bulk Phenomena, held AprIl 19-26, 1991, In
Er,ce, SIcily, Italy"--T.p. verso.
Inc 1 udes bIb II ograph, ca 1 references and Index.
1. Condensed matter--Congresses. 2. Surface chemlstry
-Congresses. 3. Cluster analysls--Congresses. 4. Chemistry,
PhYSIcal and theoretlcal--Congresses. I. Pacchlon" G.
(Glanfranco). 1954- II. 3agus. Paul S. III. Parmigiani,
Fulvlo. IV. North AtlantIC Treaty Organizat,on, Sc,ect,f,c AffaIrs
D,v,s,on. V. NATO Advanced Research Workshop on Cluster Models for
Surface and Bulk Phenomena (1991 Erlce, Italy) VI. SerIes.
OC173.4.C65C48 1992
540' .0421--dc20 91-40130
CIP
ISBN-13: 978-1-4684-6023-0 e-ISBN-13: 978-1-4684-6021-6
001: 10.1007/978-1-4684-6021-6
© 1992 Plenum Press, New York
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
It is widely recognized that an understanding of the physical and chemical
properties of clusters will give a great deal of important information relevant to surface
and bulk properties of condensed matter. This relevance of clusters for condensed
matter is one of the major motivations for the study of atomic and molecular clusters.
The changes of properties with cluster size, from small clusters containing only a few
atoms to large clusters containing tens of thousands of atoms, provides a unique way to
understand and to control the development of bulk properties as separated units are
brought together to form an extended system. Another important use of clusters is as
theoretical models of surfaces and bulk materials. The electronic wavefunctions for
these cluster models have special advantages for understanding, in particular, the local
properties of condensed matter. The cluster wavefunctions, obtained with molecular
orbital theory, make it possible to relate chemical concepts developed to describe
chemical bonds in molecules to the very closely related chemical bonding at the surface
and in the bulk of condensed matter. The applications of clusters to phenomena in
condensed matter is a cross-disciplinary activity which requires the interaction and
collaboration of researchers in traditionally separate areas. For example, it is necessary
to bring together workers whose background and expertise is molecular chemistry with
those whose background is solid state physics. It is also necessary to bring together
experimentalists and theoreticians.
This volume collects the papers presented at the NATO Advanced Research
Workshop on "Cluster Models for Surface and Bulk Phenomena" held at the Ettore
Majorana Centre, Erice, Sicily, on 19 to 26 April 1991. It represents the ideal
continuation of the 1987 Erice course "Elemental and Molecular Clusters", edited by G.
Benedek, T.P. Martin, and G. Pacchioni for Springer. This workshop brought together
87 scientists active in research related to cluster models for condensed matter. There
were 34 invited lectures and 27 poster presentations. The areas addressed were divided
into the following groups: 1. Properties of Gas-phase Clusters; II. Organometallic,
Supported Clusters and Film Growth; III. Condensed Matter: Surface Processes; and
IV. Condensed Matter: Bulk Liquids and Solids. The volume reflects the above
subdivision. Although the focus of the workshop was on the use and application of
electronic structure theory, there were important contributions from participants with
experimental backgrounds; about one-third of the invited lectures reported on
experimental research.
Several topics of important current interest and research were covered. These
included both theoretical and experimental results for high-temperature
v
superconductors and for a recently discovered form of matter, Buckmninsterfullerene
or C60. There were also discussion of technologically and socially relevant problems.
They included the characterization and growth of aerosols and their relationship to air
pollution as well as basic aspects of heterogeneous catalysis at surfaces. Fundamental
problems of long standing interest which are not' yet resolved came into discussion. As
an important example, we quote the definition and the theoretical and experimental
measurements of ionicity, in particular for adsorbate atoms and molecules on metal and
semiconductor surfaces. This broad range of topics ensures that the workshop achieved
its goal of stimulating cross-disciplinary interactions.
The workshop received support from several institutions. It was financially
sponsored by the NATO Scientific Affairs Division, but very important contributions
came from IBM Semea and from the Chemical Sciences Commettee of the Italian
National Research Council (CNR). It also benefited from the financial assistence of the
National Group for Structure of Matter, Italy, the IBM Almaden Research Center (San
Jose), the European Physical Society, and the Sicilian Regional Governement. We
gratefully acknowledge their generous support and their interest in the meeting.
The support of the Director of the Ettore Majorana Centre, Professor Antonino
Zichichi, and of the Director of the International School of Solid State Physics,
Professor Giorgio Benedek, were indispensable for the planning, organization, and
operation of the workshop. We wish to express our sincere appreciation to the center
staff, Dr. Alberto Gabriele, Dr. Pinola Savalli, and Dr. Jerry Pilarsky for their expert
assistence in all organizational matters and for their warm hospitality. The success of a
school is ultimately determined by the interest and committment of the lectureres and
particpants. We are particularly grateful to all lecturers and to the participants for their
enthusiasm and collaboration.
Gianfranco Pacchiani
Paul S. Bagus
Fulvia Parmigiani
Erice, April 1991
VI
CONTENTS
ACRONYMS •••••••••••••••••••••••••••••••••••••••••••••••• xi i i
PROPERTIES OF GAS-PHASE CLUSTERS
Subshells, Shells and Supershells in Metal Clusters 3
T.P. Martin, T. Bergmann, H. Gohlich, and T. Lange
In situ Observation of Surface Chemistry, Growth, and
Nucleation of Ultrafine particles in Gas
Suspension ••••••.•••.•••••.••.•••.••..•••••...•••• 17
H.C. Siegmann
High Temperature Molecular Dynamics Studies of Cluster
Growth and Polymer Degradation ••••••.••••••..•.••. 29
E. Blaisten-Barojas
RPA Description of optical Properties of Sodium
Microclusters ••..•••.••••.••••••••.•...••.•..••.. 41
C. Yannouleas, E. Vigezzi, P.F. Bortignon
and R.A. Broglia
Thermionic Emission of Free Tantalum Clusters ..•........ 51
T. Leisner, K. Athanassenas, o. Echt, D. Kreisle,
and E. Recknagel
Stability and Energetics of Elemental Microclusters:
Empirical Many-Body Potential Energy Function
Calculations for BCC Elements ••.•••.•••••..•••••• 59
S. Ercok and S. Katircioglu
Magnetic Properties of Free Iron and Cobalt Clusters •••• 67
P. Milani, W. de Heer, and A. Chatelain
Classical Molecular Dynamics Simulations of Small Metal
Clusters .•••••••••••••••••.••••••.••••••••.•.••.• 77
S. Sanguinetti and G. Benedek
Dynamics of Carbon Clusters: Buckminsterfullerene 87
G. Onida and G. Benedek
VII
ORGANOMETALLIC, SUPPORTED CLUSTERS AND FILM GROWTH
Clustering of metals on Semiconductor Surfaces: Relation
to Metallicity, Surface Diffusion, Growth Modes
and Schottky Barriers ...•...•.......••....••..... 99
K.E. Miyano, D.M. King, C.J. Spindt, W.E. spicer,
T. Kendelewicz, R. Cao, Z. Yu, and I. Lindau
Photoemission Studies of Supported Metal Clusters,
the Early Years .•...•..•..•....•.••.....•........ 115
M.G. Mason
Metal C~usters and Particles as Catalyst Precursors and
Catalysts •...•..••.••...•...•..•••••....•.......•. 131
H. Knozinger
Physical and Chemical Properties of High-Nuclearity
Metal-Cluster Compounds: Model Systems for Small
Metal Particles .........•............•...••.••••• 151
L.J. de Jongh, H.B. Brom, J.M. van Ruitenbeek,
R.C. Thiel, G. schmid, G. Longoni, A. Ceriotti,
R.E. Benfield and R. Zanoni
Photoelectron Spectroscopy Applied to Molecular Clusters
and Surface Clusterization Processes ........... 169
R. Zanoni
Photoemission from Size-Selected Pt-Clusters Deposited
on Silver Films •...•......•.....•................ 177
H.V. Roy, P. Fayet, F. Patthey, and W.D. Schneider
CONDENSED MATTER: SURFACE PROCESSES
Pauli Repulsion Effects in Scattering From and Catalysis
by Surfaces .•........•......•......•......••..... 189
E.J. Baerends
Theory of Surface Clusters in External Fields: Influence
of Multipole Embedding on Local Adsorbate Binding 209
K. Hermann
Theory of Core-Level Shifts of Clean and Covered
Surfaces .•............•.............•......•..... 223
o. Bisi, s. Ossicini, C. Arcangeli
Ionic Bonding of Adsorbates on Surfaces: Theoretical
Characterization and Observable Consequences .... 233
P.S. Bagus and G. Pacchioni
Chemisorption on Metal Surfaces: Cluster Model
Investigations Based on the LCGTO-LDF Method ..... 251
N. Rosch
The Use of Cluster Model for the Calculation of
Chemisorption Energetics ......................... 267
P.E.M. Siegbahn, M.A. Nygren, U. Wahlgren
Band and Cluster Models for Alkali-Semicondcutor Surfaces 281
I.P. Batra
VIII
comments on the Cluster Approach to Chemisorption .••••.• 293
R.A. van San ten and M.C. zonnevylle
CO Chemisorption on Oxide Surfaces: Bonding and
Vibrations •••••••••••.••••••••••••.•...••...••••• 305
G. Pacchioni and P.S. Bagus
Adsorption sites on Pd(110): Bridge and On-Top CO ..••••. 321
G. Blyholder and H. Sellers
Bonding of Metals to Si(lll): A Study of Chemisorption .• 333
F. Illas, J.M. Ricart, J. Rubio, J. Casanovas,
and L. Roset
Inverse Photoemission and Other Empty-state Techniques •• 349
N.V. smith
Electrochemical Contact Adsorption site Changes Driven
by Field and Charge: Fact and Theory •...••....... 359
M.R. Philpott
Theoretical Studies of Surface Reactions on Metals:
Cluster and Embedding Theory •••••••••..•••••••..• 375
J.L. Whitten
The Chemisorption Dynamics of Hydrogen on Metal Surfaces 389
G.F. Tantardini
Quantum Chemical Molecular statics Applied to Diffusion
of Ad-Atoms on Aluminium Surface ••••.••..•.••.... 405
S. Debiaggi and A. Caro
Partial optimization of Adsorbates on Clusters:
Oxygen on Al(lll) .•••.•••.•.••••....•••...•••.... 415
J. Head
Ab Initio Calculations of Stationary Points on the PES
and Determination of KIE for the Reaction of CO
with Cu20 ••••••.••••••••••••••••••••••••••••••••• 423
K. Poljanec, M. Hodosceck, and I. Kobal
Chemisorption and Magnetism: Interaction of H, C, N, 0,
with Clusters Simulating the (100) Surface of
Nickel ••••••••.•.••••••••••••••••••••••..•••••••• 433
R. Fournier, N. RUsso, D.R. Salahub, and M. Toscano
Modeling Chemisorption Processes with Metal Clusters
Systems. III. Model Thio-Alkils on Gold Surfaces • 441
H. Sellers, A. Ulman, Y. Shnidman, and J.E. Eilers
Model Studies of Chemisorption on Platinum Surfaces ••••• 453
O. Gropen, J. Almlof, and U. Wahlgren
Theoretical Study of ReH2 ..••.•.....••••.........••••.•• 463
O. SWang, K. Fregri, and O. Gropen
IX
CONDENSED MATTER: BULK LIQUIDS AND SOLIDS
X-Ray Photoelectron Spectroscopy of CuO and Nio Single
Crystals .••..••.••••...•.•....•••••..••.......•.. 475
F. Parmigiani, P.S. Bagus, anq G. Pacchioni
Ab Initio Cluster Studies of La2Cu04 ....••...••.....••.. 485
R.L. Martin
Cluster Approaches to Solid state Problems: Necessary
Complements to Band Structure Considerations ..•.. 505
W.C. Nieuwpoort and R. Broer
Ab Initio Embedded-Cluster Models of Local Defects
in Crystals •.•..••........••........•....•.••...• 515
C. Pisani, R. orlando, and R. Nada
Ab initio Studies on Zeolites and Related Catalysts •.•.. 533
J. Sauer
Cluster Models for Condensed-Phase Electron Transfer
Processes 551
M.D. Newton
Beyond the Embedded-Cluster Approximation: an Ab Initio
Treatment of Polarization Effects ..............•. 565
Z. Barandiaran and L. seijo
A Cluster Model of the Electronic Structure of Grain
Boundaries with the Impurity Segregation and
Particles Precipitation ......•.•......•.......... 577
A.Ya. Belenkii
Luminescent Properties of CuLa02 Oxide ••.....•.......... 587
H. Chermette and F. Rogemond
Cluster Simulations of Amorphous Silicon, with and
without and Impurity Boron Atom ..•............... 595
A. Fortunelli, A. De Salvo, o. Salvetti, and
A. Albertazzi
Quantum Mechanical Cluster Calculations of Solids:
the Ab Initio Perturbed Ion Method .........•..... 605
V. Luana, M. Florez, E. Francisco, A. M. Pendas,
J.M. Recio, M. Bermejo, and L. Pueyo
Ab Initio Perturbed Ion Calculations on oxo- and
F 1 uoroperovski tes ................................ 619
M. Florez, E. Francisco, V. Luana, A.M. Pendas,
J.M. Recio, M. Bermejo, and L. Pueyo
Vibrational properties of a Clustered Linear Atomic Chain
with Substitutional Impurities ....•.............. 631
M.I. Vasilevskiy and O.V. Baranova
Development of SIND01 for Extended Systems .............. 641
A. Poredda, V.A. Lovchikov, and K. Jug
x
