THE SIH4-]SIH3+H-2 REACTION - POTENTIAL-ENERGY SURFACE, RATE CONSTANTS, AND KINETIC ISOTOPE EFFECTS(H)

The potential energy surface for the gas-phase SiH4+K-->SiH3+H-2 react ion and its deuterated analogs was constructed with suitable functiona l forms to represent the stretching and bending modes, and using as ca libration criterion the reactant and product experimental properties a nd the ab initio saddle point properties. Using this surface, the rate constants were calculated with variational transition-state theory ov er the temperature range 200-1000 K, finding good agreement with exper iments. We also provide a detailed analysis of the kinetic isotope eff ects and a comparison with the scarce experimental results. (C) 1998 A merican Institute of Physics.