Quantum Chemistry Approaches to Chemisorption and Heterogeneous Catalysis

Transcription

1 Quantum Chemistry Approaches to Chemisorption and Heterogeneous Catalysis edited by F. Ruette Venezuelan Institute for Scientific Research, MC, Caracas, Venezuela KLUWER ACADEMIC PUBLISHERS DORDRECHT/ BOSTON / LONDON

2 CONTENTS PREFACE ix Ch. 1. T.H. UPTON and P.A. STEVENS, A GENERALIZED VALENCE BOND VIEW OF CHEMISORFTION AND REACTIONS ON TRANSITION METAL SURFACES 1. Introduction 3 2. Basics of the method 4 3. Studies of atomic adsorption 6 4. Molecular adsorption Dissociative adsorption Catalytic reactions and reactions on metal surfaces Future directions Limitations of the GVB method in chemisorption studies 32 Ch. 2. U. WAHLGREN and P. SIEGBAHN, A CLUSTER MODEL FOR REACTIONS ON TRANSITION METAL SURFACES 1. Introduction The role of the d orbitals The effective core potential method The chemisorption bond Cluster convergency Summary and conclusions 60

3 VI Ch. 3. D.E. ELLIS, J. GUO and JJ. LOW, INTERACTION Ot TRANSITION METAL CLUSTERS WITH ATOMS, MOLECULES AND SURFACES 1. Introduction Theoretica) modeis Response of free Cluster to a Single atom: H-NLj and H-Pt Embedded cluster-single atom interaction: H:Ni(lll) and P:Fe(lll) Response of free Cluster to molecules: H2Ni4 and H n Pt Embedded cluster-molecule interaction: C2H2:Ni(lll) Cluster-support interaction: Ni n :Ce Modification of atom-cluster interaction by support: HNi4:Ce02(l 11) Conclusion 99 Ch. 4. E.S. KRYACHKO, E.V. LUDENA and V. MUJICA, DENSITY FUNCTIONAL THEORY IN THE CONTEXT OF LOCAL-SCALING TRANSFORMATIONS AND ITS PROSPECTS FOR APPLICATIONS IN CATALYSIS 1. Drawbacks of orbital methods Some introductory considerations regarding density functional theory Advantages of density-functional-based methods The N-representability problem for reduced density matrices Local-scaling transformations and a rigorous formulation of the variational principle in density functional theory L The Kohn-Sham equations from the perspective of local-scaling transformations The Colle-Salvetti correlation energy method and local scaling transformations Non-Born-Oppenheimer treatment from the perspective of local-scaling transformations Prospects for applications of local-scaling density functional theory in catalysis 127

4 Vll Ch. 5. G. DOYEN and D. DRAKOVA, MODEL HAMILTONIAN APPRO ACH TO ADSORPTION THEORY 1. Introduction Some general criteria for model Hamiltonians Simple model Hamiltonians including correlation An elaborate model Hamiltonian for adsorption Review of important applications of the model Hamiltonian Further development and applications of the model for gas/metal surface interactions Conclusions 177 Ch. 6. G. BLYHOLDER, APPLICATION OF MINDO TO ADSORPTION AND CATALYSIS 1. Background Applications Overview 196 Ch. 7. S. BERAN and Z. SLANINA, SEMIEMPIRICAL QUANTUM- CHEMICAL STUDIES OF CATALYSTS WITH TRANSITION METALS: EHT AND RELATED APPROACHES 1. Introduction The EHT geometry optimization technique The EHT harmonic vibrational analysis Applications of the EHT program System Some illustrative applications of the CNDO/2 method Adsorption-complex isomerism 222

5 viii Ch. 8. E. SHUSTOROVICH, REACTION ENERGETICS ON TRANSITION METAL SURFACES: A BOND-ORDER CONSERVATION APPRO ACH 1. Introduction The BOC-MP model BOC-MP applications Conclusion 250 Ch. 9. F. RUETTE, A. SIERRAALTA and A.J. HERNANDEZ QUANTUM MECHANICAL CALCULATIONS OF CHEMICAL INTERACTIONS ON TRANSITION METAL SURFACES 1. Introduction Ab initio methods Density functional methods Semiempirical methods Other methods Surface dynamics Conclusions 331 INDEX 361