A PA5D (potential averaged 5D) TD (time-dependent) quantum wave-packet calculation is reported for the reaction D2 + OH → D + DOH on the Schatz-Elgersma potential energy surface. The dynamics calculation is carried out on a workstation with a modest memory, which is made possible by using a normalized angular quadrature scheme to minimize the requirement for computer memory during wave-packet propagation. Reaction probabilities, cross sections, and rate constants are presented for the title reaction, and the comparison of the present result with those of the isotopic reactions, H2 + OH and HD + OH, is given. Consistent with its isotopic reactions, the rotational orientation of D2 has a stronger effect than that of OH and, in particular, the D2 (j=1) reactant produces the largest reaction probability, which is attributed to a general steric effect. The comparison of all three isotopic reactions shows that the reactivity (reaction probability and cross section) of the HH(D) + OH system is in the order of PH(2) > PHD > PD(2). This trend is in good agreement with reduced dimensionality calculations.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry