Reaction dynamics of D+H2→DH+H: Effects of potential energy surface topography and usefulness of the constant centrifugal potential approximation

Abstract

Two findings are reported for the D+H2→DH+H reaction on the basis of the exact quantum mechanical calculation for J=0, where J is total angular momentum. First, with use of the Liu–Siegbahn–Truhlar–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 for J=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.