Theoretical and Computational Approaches to Interface Phenomena PDF
Preview Theoretical and Computational Approaches to Interface Phenomena
Theoretical 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
The list of books you might like
