Reaction dynamics of D+H2rarr;DH+H: Effects of potential energy surface topography and usefulness of the constant centrifugal potential approximation

摘要

Two findings are reported for the D+H2rarr;DH+H reaction on the basis of the exact quantum mechanical calculation forJ=0, whereJis total angular momentum. First, with use of the Liundash;Siegbahnndash;Truhlarndash;Horowitz (LSTH) surface and the Varandas surface, we demonstrate that a rather small difference in potential energy surface (PES) induces a surprisingly large effect on reaction dynamics. Two origins of the discrepancy are pointed out and analyzed: (1) Noncollinear conformation in the reaction zone contributes to the reaction significantly despite the fact that the minimum energy path and the saddle point are located in the collinear configuration. (2) A difference in the distant part of PES also causes a discrepancy in the reaction dynamics indirectly, although this effect is much smaller than (1). Secondly, we investigate the validity of the constant centrifugal potential approximation (CCPA) based on the accurate results forJ=0. The use of CCPA to estimate total cross section and rate constant is again proved to have practical utility as in the cases of the sudden and adiabatic approximations.