Direct dynamics studies on the isomerization and H 2 elimination reactions of H 3PS

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Direct ab initio dynamics methods are using to study the H 3 PS → 1 trans - H 2 PSH → 2 cis - H 2 PSH , and H 3 PS → 3 HPS + H 2 → 4 PSH + H 2 reactions. The minimum energy paths (MEPs) of the two reaction channels, geometries, and harmonic vibrational frequencies for all stationary points and selected points along the MEPs are calculated using the QCISD/6-311++G(d,p) method. The single-point calculations are carried out by QCISD(T)/6-311++G(2df,2pd). The fitted three-parameter expressions of the calculated CVT/SCT and TST/Eckart rate coefficients in 200–2000 K for reactions (1) and (3) are k 1 CVT / SCT = 2.69 × 10 - 42 T 16.52 exp ( - 9811.9 / T ) s - 1 , k 1 TST / Eckart = 1.27 × 10 - 31 T 13.39 exp ( - 12180.6 / T ) s - 1 , k 3 CVT / SCT = 8.93 × 10 - 20 T 9.82 exp ( - 20612.1 / T ) s - 1 , and k 3 TST / Eckart = 1.31 × 10 - 26 T 11.86 exp ( - 18896.4 / T ) s - 1 , respectively.