Table Of ContentTheoretical and
Computational Approaches
to Interface Phenomena
Theoretical and
Computational Approaches
to Interface Phenomena
Edited by
Harrell Lee Sellers
South Dakota State University
Brookings, South Dakota
and
Joseph Thomas Golab
Amoco Research Center
Naperville, Illinois
Springer Science+Business Media, LLC
Library of Congress Cataloging-in-Publication Data
Theoretical and computational approaches to interface phenomena /
edited by Harrell Lee Sellers and Joseph Thomas Golab.
p. cm.
"Proceedings of an International Conference on Theoretical and
Computational Approaches to Interface Phenomena, held August 2-4,
1993, in Brookings, South Dakota'—T.p. verso.
Includes bibliographical references and index.
1. Interfaces (Physical sciences)—Congresses. 2. Interfaces
(Physical sciences)—Computer simulation—Congresses. I. Sellers,
Harrell Lee. II. Golab, Joseph Thomas. III. International
Conference on Theoretical and Computational Approaches to Interface
Phenomena (1993 : Brookings, S.D.)
QC173.4.I57T48 1995
541.3'3—dc20 95-1410
CIP
Proceedings of an International Conference on Theoretical and Computational Approaches to
Interface Phenomena, held August 2-4, 1993, in Brookings, South Dakota
ISBN 978-1-4899-1321-0 ISBN 978-1-4899-1319-7 (eBook)
DOI 10.1007/978-1-4899-1319-7
© Springer Science+Business Media New York 1994
Originally published by Plenum Press, New York in 1994
Softcover reprint of the hardcover 1st edition 1994
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
Many chemical processes that are important to society take place at
boundaries between phases. Understanding these processes is critical in order
for them to be subject to human control. The building of theoretical or
computational models of them puts them into a theoretical framework in terms of
which the behavior of the system can be understood on a detailed level.
Theoretical and computational models are often capable of giving descriptions of
interfacial phenomena that are more detailed, on a molecular level, than can be
obtained through experimental observation. Advances in computer hardware
have also made possible the treatment of larger and chemically more interesting
systems.
The study of interfacial phenomena is a multi-disciplinary endeavor which
requires collaboration and communication among researchers in different fields
and across different types of institutions. Because there are many important
problems in this field much effort is being expended to understand these
processes by industrial laboratories as well as by groups at universities. Our
conference titled "Theoretical and Computational Approaches to Interface
Phenomena" held at South Dakota State University, August 2-4, 1993 brought
together over thirty scientists from industry and academia and three countries in
the western hemisphere to discuss the modeling of interfacial phenomena.
Important topics discussed at this conference and within the pages of this book
are: heterogeneous catalysis, surface diffusion, electrochemical phenomena,
solvation, self-assembling organic films, chemisorption processes and
manipulation of surface properties. It is our hope that this book will contribute to
the activity level and the development of the field.
We are indebted to the sponsors of the conference without whose help the
conference would not have been possible. We thank Cray Research, Inc. for their
high level of participation. The conference was sponsored by the IBM
Corporation, Biosym Technologies, the South Dakota EPSCoR program of the
National Science Foundation, Amoco Chemical Company and South Dakota State
University.
Harrell Sellers
Brookings, South Dakota
Joseph Golab
Naperville, Illinois
May 1994
v
CONTENTS
Acronyms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Reaction Path Approach to Dynamics at a Gas-Solid Interface: Quantum
Tunneling Effects for an Adatom on a non-rigid Metallic Surface ...... 1
S.E. Wonchoba, W.-P. Hu and D. G. Truhlar
Catalysis Modeling Employing Ab Initio and Bond Order Conservation -
Morse Potential Methods ...................................... 35
H. Sellers
Computer Simulations of Excitable Reaction-Diffusion Systems ...... . 57
M.R. Hoffmann and S.P. Muller
Molecular Dynamics Computer Simulations of Charged Metal Electrode -
Aqueous Electrolyte Interfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
M.R. Philpott and J.N. Glosli
Molecular Dynamics Computer Simulations of Aqueous Solution/Platinum
Interface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
M.L. Berkowitz and L. Perera
Diffusion Mechanisms of Flexible Molecules on Metallic Surfaces 119
M. Silverberg
Computer Simulation of Solvation in Supercritical Fluids ............ 131
G.S. Anderson, KM. Hegvik and M.R. Hoffmann
Structure-Function Modeling in Blood Coagulation: Interfaces, Biology
and Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
M.N. Liebman
Domains and Supedattices in Self-Assembled Monolayers of Long-Chain
Molecules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
J. Hautman and M.L. Klein
Manipulating Wetting and Ordering at Interfaces by Adsorption of
Impurities .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
D.J. Olbris and Y. Shnidman
vii
Density Functional Description of Metal-Metal and Metal-Ligand Bonds. 187
D.R. Salahub, M. Castro, R. Fournier, P. Calaminici, N. Godbout,
A. Goursot, C. Jamorski, H. Kobayashi, A. Martinez, I. Pdpai,
E. Proynov, N. Russo, S. Sirois, J. Ushio and A. Vela
Density Functional Studies of Boron Substituted Zeolite ZSM-5 219
M.S. Stave and J.B. Nicholas
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
viii
ACRONYMS
ACE Allis-Chalmers Enthusiast
AE All Electron
AFM Atomic Force Microscopy
ATC Amoco Technology Company
BDA Bond Dihedral Angle
BDE Bond Dissociation Energy
BOC Bond Order Conservation; Bond Order Constraint
BOC-MP Bond Order Conservation -Morse Potential
BP Becke Perdew (Exchange Correlation Functional)
ESSE Basis Set Superposition Error
CCDB Cambridge Crystalographic Data Bank
CD Charge Density; Crystalographic Diffraction
CD-SCSAG Centrifugal Dominant Small Curvature Semi-classical
Adiabatic Ground State
CI Configuration Interaction
CN Crank-Nicholson
CS (Hard Sphere Expansion) Conformal Solution
CSOV Constrained Space Orbital Variance
DB Dynamical Bottleneck
DFT Density Functional Theory
DN Double Numerical
DNP Double Numerical with Polarization
DMP Dynamic Morse Potential
DZVP Double Zeta plus Valence Polarization
EAM Embedded Atom Method
ECP Effective Core Potential
EMBL European Molecular Biology Laboratory
ESCA Electron Spectroscopy for Chemical Analysis
ESR Electron Spin Resonance
EV Excluded Volume
FCC Face Centered Cubic
FIX Factor IX
FTCS Forward Time Center Space
FT-IR Fourier Transform -Infrared Spectroscopy
GB GenBank Database
GIXS Grazing Incidence X-ray Scattering
G-L Greer-Levitt (Algorithm)
GS Ground State
GTO Gaussian Type Orbital
GVB Generalized Valence Bond
HF Hartree-Fock
HFS-LCAO Hartree-Fock-Slater Linear Combination of Atomic
Orbitals
HMB Hemoglobin Mutation Bank
IHP Inner Helmholtz Plane
IP Ionization Potential
ix
IR Infrared (Spectroscopy)
IRAS Infrared Reflection Absorption Spectroscopy
KS Kohn-Sham (Functions,Theory)
K-S Kabsch -Sanders (Algorithm)
LC Local Composition
LCAO Linear Combination of Atomic Orbitals
LCGTO-DFT Linear Combination of Gaussian Type Orbitals -
Density Functional Theory
LCGTO-LSD Linear Combination of Gaussian Type Orbitals -
Local Spin Density (Approximation)
LDA Local Density Approximation
LDP Linear Distance Plot
LEED Low Energy Electron Diffraction
LSDA Local Spin Density Approximation
MC Monte Carlo (Method)
MCP Model Core Potential
MCSCF Multiconfigurational Self-Consistent Field
(Approximation)
MD Molecular Dynamics (Classical)
MEP Minimum Energy Path
MES Minimum Energy Site
MNDO Modified Neglect of Differential Overlap
MO Molecular Orbital
MP2 M~ller-Plesset (Second Order) Perturbation Theory
MRSDCI Multi-Reference Singles and Doubles Configuration
Interaction
NCBI National Center for Biotechnology Informatics
NL Non-Local
NMR Nuclear Magnetic Resonance
NN Nearest Neighbor
NNB Nearest Neighbor Bonding
OHP Outer Helmholtz Plane
PA Proton Affinity
PC Point Charge
PDB Protein Database (Data Bank)
PDE Partial Differential Equation
PEP Pauli Exclusion Principle
PERI Protein Engineering Research Institute
PES Potential Energy Surface
PIR Protein Identification Resource
PI-TST Path Integral Transition State Theory
PMF Potential Mean Force
PN Patri Net
RECP Relativistic Effective Core Potential
RHF Restricted Hartree-Fock (Theory)
SAM Self-Assembled(ing) Monolayers
SCF Self-Consistent Field (Theory)
SCT Small Curvature Tunneling
SEXAFS Surface Extended X-ray Absorption
STM Scanning Tunneling Microscopy
TM Transition Metal
TMA Trimethylamine
TST Transition State Theory
TST-QEP Transition State THeory with Quantum Effective
Potentials
VWN Vosko, Wilk and Nusair (Exchange Correlation
Functional)
XC Exchange Correlation
XPS X-ray Photoelectron Spectroscopy
XSW X-ray Standing Wave
x
REACTION PATH APPROACH TO DYNAMICS
AT A GAS-SOLID INTERFACE:
QUANTUM TUNNELING EFFECTS FOR AN ADA TOM
ON A NON-RIGID METALLIC SURFACE
Steven E. Wonchoba, Wei-Ping Hu, and Donald G. Truhlar
Department of Chemistry and Supercomputer Institute
University of Minnesota, Minneapolis, MN 55455-0431
1. INTRODUCTION
Chemical reactions occurring on metal surfaces are of great technological importance,
especially for catalysis. 1-6 Diffusion of reagents on the surface is a critical step in many such
reactions.I,2·7-9 Surface diffusion is also important in molecular beam epitaxy, chemical vapor
deposition, and controlled growth of thin films. 10 Diffusion of hydrogen atoms is particularly
interesting from a theoretical point of view because of the large quantum mechanical tunneling
contributions to this process. 1 1-38 Laser-induced thermal desorption, field emission
tluctuation, and linear optical diffraction techniques have been used to study hydrogen diffusion
on several metals, including Ni. W, Ru, Pt, Rh, and Cu.39-62 Theoretical studies of these
processes can complement the data available from these expellments and can eventually be used
to study subsurface and bulk diffusion processes more accurately than may be allowed by
current experiments. These subsurface and bulk processes are fundamental for energy storage
and fuel cell development, hydrogen embrittlement, and the possibility of subsUIface hydrogen
in catalysis.
Under a broad range of conditions one can model sUIface diffusion of adsorbed atoms as a
unimolecular chemical reaction in which the chemisorption or physisorption bonds of the
adatom at an initial site are broken and new bonds are formed at another site. The system
composed of the adatom bound at the initial site is called the reactant, and the system composed
of the adatom bound at the final site is called the product.
In Section 2 we provide an overview of the reaction-path approach for calculating rate
constants of chemical reactions that involve large tunneling effects. We assume that the nuclear
