Quantum mechanical rate constants for the D + H 2 → HD + H reaction on the BKMP2 potential energy surface

Abstract

Converged quantum mechanical cumulative reaction probabilities for the D + H 2 → HD + H reaction have been calculated on the latest Boothroyd-Keogh-Martin-Peterson (BKMP2) potential energy surface (PES) using the log-derivative Kohn variational principle. The separable rotation approximation of Mielke, Lynch, Truhlar and Schwenke has been applied to obtain thermal rate constants between 167 and 1500 K. The low-temperature rate constants are about 8% smaller than those calculated on the BKMP PES, but are still significantly higher than the experimental values. It is suggested that new experimental measurements in the low to intermediate temperature range (below 1000 K) are necessary for a definitive assessment of the PES.