This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr- sitions and thermodynamic properties in general. A number of excellent revIew articles, listed in the bibliography, cover this material. Likewise, little is said about scattering off solid surfaces; this subject is again covered in several books and many review articles. Lastly, little is said about chemisorption kinetics, for which microscopic thebries and models have not been fully developed but are still at a rather early exploratory stage.
Table of Contents1. Introduction.- 1.1 Adsorption Phenomena: a Brief Survey.- 1.2 Survey of Experimental Methods.- 2. Gas-Solid Interaction.- 2.1 The Static Surface Potential Vs(r).- 2.2 Mean-Field Surface Potential at Finite Coverage.- 2.3 The Dynamic Atom-Solid Interaction.- 2.4 Phonon Dynamics of a Solid.- 2.5 The Gas-Solid Hamiltonian.- 3. The Master Equation.- 3.1 The Mesoscopic Approach to the Master Equation.- 3.2 The Master Equation for Physisorption Kinetics.- 3.3 The Microscopic Approach to the Master Equation.- 3.4 The Master Equation at Finite Coverage.- 4. Transition Probabilities in the Master Equation.- 4.1 One-phonon Processes at Low Coverage.- 4.2 Multi-phonon Processes and Correlation Functions.- 4.3 Soft Cube Model and Phenomenological Models at Low Coverage.- 4.4 Mean-Field Theory at Finite Coverage.- 5. Desorption Times.- 5.1 Model System with Two Bound States.- 5.2 Systems with a Few Shallow Bound States.- 5.3 Perturbation Theory of the Master Equation.- 5.4 Desorption Kinetics Mediated by Surface Phonons.- 5.5 Inclusion of Parallel Phonon Momentum for Mobile Desorption.- 5.6 Desorption from a Localized Adsorbate.- 5.7 Cole-Toigo Corrections.- 5.8 Multiphonon Contributions.- 5.9 Multilayer Desorption.- 5.10 Adsorbent Cooling in Thermal Desorption.- 5.11 Flash Desorption and Thermalization.- 6. Time of Flight Spectra.- 6.1 Experiments.- 6.2 Flux of Desorbed Particles.- 6.3 One-phonon Processes.- 6.4 Classical Models.- 7. Sticking and Accommodation.- 7.1 Experimental Results.- 7.1.1 Sticking Coefficient.- 7.1.2 Accommodation Coefficient.- 7.2 Theory.- 7.2.1 Sticking.- 7.2.1(a) Quantum Theories of Sticking.- 7.2.1(b) Classical Theories of Sticking.- 7.2.2 Energy Accommodation.- 7.2.2(a) Quantum Theories of Accommodation.- 7.2.2(b) Classical Theories of Accommodation.- 8. Kramers Equation.- 8.1 Derivation from the Master Equation.- 8.2 Macroscopic Laws.- 8.3 Friction Coefficient.- 8.4 Hydrodynamics of Adsorption.- 9. Summary and Outlook.- 9.1 Progress and Problems.- 9.2 Related Topics I: Photodesorption.- 9.3 Related Topics II: Electron-Stimulated Desorption.- 9.4 Approaches to Chemisorption Kinetics.- References.