Application of transition-state theory to gas-surface reactions: Barrierless adsorption on clean surfaces

Pitt, I.G., Gilbert, R.G. and Ryan, K.R. (1994) Application of transition-state theory to gas-surface reactions: Barrierless adsorption on clean surfaces. Journal of Physical Chemistry, 98 49: 13001-13010.


Author Pitt, I.G.
Gilbert, R.G.
Ryan, K.R.
Title Application of transition-state theory to gas-surface reactions: Barrierless adsorption on clean surfaces
Journal name Journal of Physical Chemistry   Check publisher's open access policy
ISSN 0022-3654
1541-5740
Publication date 1994-12
Sub-type Article (original research)
DOI 10.1021/j100100a031
Volume 98
Issue 49
Start page 13001
End page 13010
Total pages 10
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract Transition-state theory (TST) has long been applied to gas-surface reactions for the purpose of characterizing and predicting desorption rate coefficients. However, current perceptions of its use exclude the use of TST from meaningful description of the sticking coefficient, either for clean or for partially covered surfaces, principally because of the limitations of the theory in describing adsorbate-adsorbent energy transfer. TST has thus previously been neglected as an interpretative and predictive tool for the temperature and coverage dependence of the sticking coefficient, particularly for processes without a barrier to adsorption. It has previously been generally believed that only variational minimum dividing surfaces at infinite adsorbate-surface separation could be possible for barrierless adsorption processes, implying a TST sticking coefficient of unity. Reassessment of this point suggests that this is not necessarily the case even for clean surfaces; a form for the desorption rate coefficient that insists all trajectories have sufficient energy to desorb is derived, and a model calculation of the temperature dependence of the sticking coefficient on a clean surface is presented that demonstrates that other variational minimum dividing surfaces are indeed possible.
Keyword Dependent desorption-kinetics
Pre-exponential factor
Carbon-monoxide
Theoretical-analysis
Reaction dynamics
Coverage
Diffusion
Hydrogen
Co
Chemisorption
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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