Chem. Phys. Lett. 693, 66-71 (2018)

Tunneling and reflection in unimolecular reaction kinetic energy release distributions

K. Hansen

Center for Joint Quantum Studies and Department of Physics, Tianjin University, Tianjin 300072, China

Department of Physics, Gothenburg University, 41296 Gothenburg, Sweden

Abstract

The kinetic energy release distributions in unimolecular reactions is calculated with detailed balance theory, taking into account the tunneling and the reflection coefficient in three different types of transition states; (i) a saddle point corresponding to a standard RRKM-type theory, (ii) an attachment Langevin cross section, and (iii) an absorbing sphere potential at short range, without long range interactions. Corrections are significant in the one dimensional saddle point states. Very light and lightly bound absorbing systems will show measurable effects in decays from the absorbing sphere, whereas the Langevin cross section is essentially unchanged.