Ab initio mechanism and thermal rate constants for the reaction of atomic H with Ge2H6
Abstract
The reaction of digermane Ge2H6 with atomic H has been studied theoretically. The detailed mechanism has been revealed for the first time. This reaction involves not only abstraction but also substitution. The calculation shows that there are two transition states for the substitution reaction: (1) frontside attack of the Ge–Ge bond by the hydrogen atom and (2) backside attack of the GeH3 group by the hydrogen atom along the Ge–Ge axis, forming a transition state structure with C3v symmetry. Changes of geometries, generalized normal-mode vibrational frequencies, and potential energies along the reaction path for each channel are discussed and compared. On the basis of the ab initio data, the rate constants of each channel have been deduced by canonical variational transition state theory (