The Chemical Physics of Surfaces

1. Introduction.- 1.1. Surface States and Surface Sites.- 1.1.1. The Chemical Versus Electronic Representation of the Surface.- 1.1.2. The Surface State on the Band Diagram.- 1.1.3. The Fermi Energy in the Surface State Model.- 1.1.4. Need for Both Surface Site and Surface State Models.- 1.2. Bonding of Foreign Species to the Solid Surface.- 1.2.1. Types of Interaction.- 1.2.2. The Chemical Bond.- 1.2.3. Acid and Basic Surface Sites on Solids.- 1.2.4. Adsorbate Bonding on Various Solid Types.- 1.2.5. Movement of Surface Atoms: Relaxation, Reconstruction, and Relocation.- 1.2.6. The Electronic Energy Level (Surface State) of a Sorbate/Solid Complex.- 1.3. Surface Hydration on Ionic Solids.- 1.4. Surface Heterogeneity.- 2. Space Charge Effects.- 2.1. General.- 2.1.1. The Double Layer Involving Two Planar Sheets of Charge.- 2.1.2. The Space Charge due to Immobile Ions: The Depletion Layer.- 2.1.3. The Double Layer in the Band Diagram, Fermi Energy Pinning.- 2.2. Space Charge Effects with Reactive Surface Species.- 2.2.1. The Accumulation Layer.- 2.2.2. The Inversion Layer.- 2.3. Electron and Hole Transfer between the Solid and Its Surface.- 2.3.1. Basic Physical Model of Electron and Hole Capture or Injection.- 2.3.2. Electron and Hole Transfer with Large Changes in the Surface Barrier.- 2.3.3. Charge Transfer to a Surface Species in a Polar Medium: The Fluctuating Energy Level Mechanism.- 3. Experimental Methods.- 3.1. Surface Measurements Based on Electrical and Optical Techniques.- 3.1.1. Work Function.- 3.1.2. Surface Conductivity.- 3.1.3. Electroreflectance.- 3.1.4. Field Effect.- 3.1.5. Surface Photovoltage.- 3.1.6. Capacity of the Double Layer.- 3.1.7. Channel Measurements.- 3.1.8. Powder Conductance.- 3.1.9. Ellipsometry.- 3.1.10. Other Electrical and Optical Measurements.- 3.2. The Surface Spectroscopies.- 3.2.1. Ultraviolet Photoelectron Spectroscopy (UPS).- 3.2.2. Energy Loss Spectroscopy (ELS).- 3.2.3. Soft X-Ray Appearance Potential Spectroscopy (SXAPS).- 3.2.4. Field Emission (FEM).- 3.2.5. Field Ion Microscopy (FIM).- 3.2.6. Ion Neutralization Spectroscopy (INS).- 3.2.7. Low-Energy Electron Diffraction (LEED).- 3.2.8. Methods of Chemical Composition Determination for the Surface.- 3.2.9. Studies of Chemical Reactions due to the Impinging Beam.- 3.3. Chemical Measurements.- 3.3.1. Infrared Absorption.- 3.3.2. Temperature-Programmed Desorption.- 3.3.3. Adsorption of Gaseous Acids and Bases or of Indicators.- 4. The Adsorbate-Free Surface.- 4.1. Introduction.- 4.1.1. The Classification of Solids.- 4.1.2. Preparation of a Clean Surface.- 4.2. Theoretical Models.- 4.2.1. Quantum Models.- 4.2.2. Semiclassical Models: The Madelung Model for Ionic Solids.- 4.2.3. Models for Electron Pair Sharing: Lewis and Bronsted Sites.- 4.2.4. Comparison of the Various Surface States and Sites.- 4.3. Measurements on Adsorbate-Free Ionic Solids.- 4.3.1. Reconstruction on Ionic Solids.- 4.3.2. Physical Measurements on Ionic Solids.- 4.3.3. Chemical Measurements on Ionic Solids.- 4.4. Measurements on Adsorbate-Free Covalent or Metallic Solids.- 4.4.1. Reconstruction on Covalent and Metallic Solids.- 4.4.2. Electrical Measurements of Intrinsic Surface States on Covalent Solids.- 4.4.3. Measurement by the Surface Spectroscopies.- 5. Bonding of Foreign Species at the Solid Surface.- 5.1. Reconstruction and Relocation in Bonding.- 5.2. The Semiclassical Model of Bonding: The Surface Molecule.- 5.2.1. Surface Molecule Versus Rigid Band Model.- 5.2.2. Adsorbate Bonding to Covalent or Metallic Solids.- 5.2.3. Adsorbate Bonding to Ionic Solids.- 5.2.4. Multilayer Adsorption: The Development of a New Phase.- 5.3. Quantum Models of the Adsorbate/Solid Bond.- 5.3.1. Solid State Theories: The Semi-infinite Crystal.- 5.3.2. Cluster Models.- 5.3.3. The Interacting Surface Molecule (the Model Hamiltonian Analysis).- 5.3.4. Other Quantum Models.- 5.3.5. Remarks.- 5.4. Measurement of Adsorbate Surface States on Covalent or Metallic Solids.- 5.4.1. Scre