Theoretical Heterogeneous Catalysis

The following sections are included:

• PREFACE

• CONTENTS

For many industrial chemical processes catalysis is essential. Innovations in catalysis have minimized usage of energy and raw material usage and will become of increasing importance for the production of chemicals and in the drive to cut environmental wastage. In many industrial laboratories as well as universities catalysis is extensively investigated. The approaches differ depending on the particular aspects of catalysis being researched…

The following sections are included:

• Introduction

• Theoretical Intermezzo 1. Background to the Extended-Hückel Method and other Semi-Empirical Methods

• Elementary Theory of Chemisorption. One-Dimensional Models
  • ELEMENTARY FREE-ELECTRON GAS MODELS
  • TIGHT-BINDING CALCULATIONS, ALL ATOMS EQUAL; NO HYBRIDIZATION
  • ONE-DIMENSIONAL MODELS, HYBRIDIZATION
    • Physical background
    • Elementary quantum chemistry of the Shockley surface state

• Theoretical Intermezzo 2. Introduction to the Green's Function Method, Application to One-Dimensional Surfaces
  • GREEN'S FUNCTION CALCULATION OF LOCAL DENSITY OF STATES OF OPEN CHAIN
  • THE RESOLVENT METHOD. APPLICATION TO SHOCKLEY SURFACE STATE

• Elementary Quantum Chemistry of Chemisorption to Metal Surfaces. Tamm Surface States, Surface Molecule Limit
  • A MODEL FOR THREE-DIMENSIONAL CHEMISORPTION, BETHE LATTICE APPROXIMATION; THE CONCEPT OF GROUP ORBITALS

• Theoretical Intermezzo 3. Formal Chemisorption Theory
  • THE EXPRESSIONS FOR THE BOND ENERGY
  • RELATIONSHIP WITH HOMO-LUMO AND FRONTIER ORBITAL THEORY
  • RELATIONSHIP WITH BOND-ORDER CALCULATIONS

• The Effect of Electron-Electron Interactions
  • THE UNRESTRICTED VERSUS THE RESTRICTED HARTREE-FOCK APPROXIMATION
  • THE UNRESTRICTED HARTREE-FOCK SOLUTION OF THE NEWNS-ANDERSON CHEMISORPTION MODEL
  • THE EFFECTIVE ONE-CENTER ELECTRON-ELECTRON REPULSION INTEGRAL. TIME-DEPENDENT CHARGE FLUCTUATIONS OF THE CHEMISORBED STATE
    • The physical picture

• Application of Bethe Lattice Method to CO and H Chemisorption
  • THE VALENCE ELECTRON STRUCTURE OF A TRANSITION METAL SURFACE
  • ATOP AND BRIDGE COORDINATION OF CO AND H
  • COORDINATION OF CO TO DIFFERENT F.C.C. TRANSITION METAL SURFACES

• Free-Electron Approaches to Chemisorption. Some First-Principle Calculations

• References

The following sections are included:

• Introduction

• Trends in Chemisorption
  • ADSORPTION ENERGY AS A FUNCTION OF COVERAGE; SURFACE RECONSTRUCTION

• Quantum Chemistry of Surface Dissociation and Association Reactions

• Shustorovich's Empirical Approach to Surface Association and Dissociation Reactions
  • THE SHUSTOROVICH BOND ORDER CONSERVATION METHOD
  • DERIVATION OF THE FORMULA FOR THE HEAT OF MOLECULAR ADSORPTION
  • DERIVATION OF THE FORMULA REPRESENTING THE ACTIVATION ENERGY FOR DISSOCIATION OF A CHEMISORBED MOLECULE

• Catalysis of Synthesis Gas Conversion
  • GENERAL FEATURES
  • QUANTUM CHEMISTRY OF CO CHEMISORPTION AND DISSOCIATION
  • CH_x; FRAGMENT CHEMISORPTION AND REACTIVITY

• Hydrocarbon Conversion Catalysis
  • GENERAL BACKGROUND
  • THEORY OF SURFACE LIGAND EFFECTS
  • QUANTUM CHEMISTRY OF CATION-INDUCED CHANGES IN CHEMISORPTION TO METAL CLUSTERS

• Selective Oxidation Catalysis
  • GENERAL BACKGROUND
  • QUANTUM CHEMISTRY OF CHEMISORPTION OF THE 0₂ MOLECULE TO SILVER
  • EPOXIDATION OF ETHYLENE; THE ELECTRONIC BASIS OF THE ROLE OF SUB-SURFACE OXYGEN

• References

The following sections are included:

• General Physicochemical Properties of the Ionogenic Surface. Pauling's Valency Concept
  • SURFACE RELAXATION EFFECTS
  • THE MADELUNG POTENTIAL OF THE SURFACE LAYER; PAULING'S VALENCIES
    • Ion charge excess of the dense TiO₂ surface
    • Elementary theory of surface Brønsted and Lewis acidity and basicity. Implications for catalyst preparation and acid catalysis

• The Electronic Structure of Transition-Metal Oxide Surfaces
  • LIGAND-FIELD THEORETICAL CONSIDERATIONS, THE SURFACE DANGLING BOND ANALOG
  • VALENCE ELECTRON STRUCTURE OF THE RUTILE SURFACES

• Quantum-Chemical Basis of Brønsted Acidity in Zeolites

• The Quantum-Chemical Basis of Heterogeneous Oxide Catalysis

• References

The following sections are included:

• Introduction

• Gibbs' Rule
  • SURFACE COMPOSITION OF ALLOYS
    • General features
  • STATISTICAL-MECHANICAL THEORY OF SURFACE ENRICHMENT IN ALLOYS
    • Regular solution model for a two-component alloy
  • APPLICATION OF THE CLUSTER METHOD

• Lattice Stability of Zeolites
  • BACKGROUND
  • THE LATTICE ENERGY OF ZEOLITES
    • Zeolitic SiO₂ polymorphs
    • Zeolite lattice energy as a function of Al content
    • Adsorption of molecules in zeolites

• Fractals in Catalysis

• References

The following sections are included:

• SUBJECT INDEX