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J. Vac. Sci. Technol. B 2, 550 (1984); http://dx.doi.org/10.1116/1.582837 (11 pages)

Classical stochastic diffusion theory for thermal desorption from solid surfaces

Antonio Redondo1, Yehuda Zeiri2, and William A. Goddard2

1Electronics Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
2Arthur A. Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125

As a first step in the microscopic study of dynamic processes on surfaces and at interfaces, we have considered the thermal desorption of adsorbed species on solid surfaces. We review recent developments based on a classical stochastic diffusion formulation. Using this theory, we obtained a simple rate expression, R=(Ω0/2π) f(T)exp(−De/kT), where Ω0 is the surface‐adsorbate vibrational frequency and De the dissociation energy. For atoms f(T)=1, whereas for molecules f(T) depends on the parameters for the frustrated rotations at the surface. The effect of coverage on the rate of desorption and the process of desorption into a fluid are also examined. Finally, we discuss the relationship between our theory and the expressions obtained from activated complex (transition‐state) theory.

KEYWORDS and PACS

PACS

  • 68.03.Fg

    Evaporation and condensation of liquids

  • 68.43.Mn

    Adsorption kinetics

  • 68.43.-h

    Chemisorption/physisorption: adsorbates on surfaces

PUBLICATION DATA

ISSN

0734-211X (print)  

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