Theory of Field Desorption

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Abstract
The theory of field desorption proposed previously has been extended by a more detailed quantum‐mechanical calculation of the rate constants of desorption for various cases, including an attempt to evaluate matrix elements for the electronic transition when the latter is slow. A simple, generalized model of chemisorption on metals is presented and used in these calculations. It is found that two‐electron transitions lead to somewhat smaller rate constants than one‐electron transitions, but that the effect is not very large. In general, a one‐dimensional theory leads to rate constants with essentially normal pre‐exponential terms, except under conditions where adsorbate tunneling becomes important. A tentative explanation for the compensation effect, i.e., decreases in pre‐exponential term with decreasing activation energy observed experimentally in a number of different cases, is given in terms of changes of reaction path with temperature.

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