Abstract
It is generally known that the initial sticking probabilities of nitrogen on iron single-crystal planes are extremely low although the corresponding activation barriers are not high or even negligible. It implies that the dissociative adsorption of nitrogen is accompanied by strong entropy barriers. In this work, these entropy barriers are interpreted in terms of a special orientation of nitrogen molecules necessary to undergo dissociative adsorption. The applied model is based on the statistical rate theory combined with the quasi-chemical interaction term in order to account for possible intermolecular interaction effects. Analysis of the model parameters led to a few important conclusions. Namely, adsorption on Fe(111) is more sensitive to the orientation of the nitrogen molecule than that on Fe(100); the frequency of getting the correct orientation is ca. 3 times greater on Fe(100) than that on Fe(111). However, the initial sticking coefficient is still ca. 1 order of magnitude smaller in the case of ...
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