Quantum Theory for the Unimolecular Rate Constant

摘要

A formal quantum theory for the unimolecular rate constant is presented. This theory is an elaboration on an earlier paper by Wilson and Thiele. The theory treats the unimolecular breakdown quantum mechanically, but retains two classicalhyphen;like assumptions concerning the collision mechanism and the criteria for reaction. A model calculation suggests that these assumptions can be used if ohgr;Lt;kT/h. Some arguments are also presented which suggest this same limit of applicability for the general theory.