A Monte Carlo evaluation of thermal desorption rates

摘要

The recently reported method for computing thermal desorption rates via a Monte Carlo evaluation of the appropriate transition state theory expression lsqb;J. E. Adams and J. D. Doll, J. Chem. Phys. 74, 1467 (1980)rsqb; is extended, by the use of importance sampling, so as to generate the complete temperature dependence in a single calculation. We also describe a straightforward means of calculating the activation energy for the desorption process within the same Monte Carlo framework. The result obtained in this way represents, for the case of a simple desorptive event, an upper bound to the true value.