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本文基于2022年报道的一个SiH2（11A'）势能面，运用切比雪夫波包方法对H(2S)+SiH (X2П; v=0,j=0)→Si(1D)+H2(X1Σ<i>g+)反应体系在1.0×10-3~1.0 eV的碰撞能量范围内进行了动力学研究。分别应用忽略科里奥利耦合效应的耦合态近似和精确量子力学计算得到该反应的反应几率、积分散射截面和速率常数。计算发现在 J 较大时科里奥利耦合效应显著提升该反应的反应几率，忽略科里奥利耦合效应会使H +SiH 反应的积分散射截面和速率常数减小，对于速率常数而言，温度越高，两种计算方法所得结果的差距越大。精确的量子力学计算结果表明，H +SiH 反应的速率常数在300 -1000 K之间几乎不随温度改变，这与H+CH 反应非常相似，但是在数值上，前者比后者大一个数量级。Initial state-selected and energy resolved reaction probabilities, integral cross sections（ICS） and the thermal rate constants of the H(2S)+SiH (X2П; v=0,j=0)→Si(1D)+H2(X1Σ<i>g+) reaction are calculated within coupled states（CS） approximation and accurate calculation with full Coriolis coupling（CC） by a time-dependent wave packet propagation method (Chebyshev wave packet method). The new ab initio global potential energy surface (PES) of the electronic ground state (11A') of the system, recently reported by Li et al. [Phys. Chem. Chem. Phys., 2022, 24, 7759], is employed for the purpose. All partial wave contributions up to the total angular momentum J=80 for CS approximation and J=90 for CC calculation are considered to obtain the converged ICSs over a collision energy range of 1.0×10-3-1.0 eV. The calculated probabilities and ICSs display a decreasing trend with the increase of the collision energy and show an oscillatory structure due to the SiH2 well on the reaction path. The neglect of CC effect will lead to underestimation of the ICS and the rate constant due to the formation of a SiH2 complex supported by the stationary points of the SiH2（11A'）PES. In addition, the results of the exact calculation including CC effect are compared with those from the CS approximation. For the reaction probability, a similar trend of CC and CS calculations are observed at small total angular momentum J=10, 20 and 30, and the CC results are larger than the latter almost in the whole considered energy range at large total angular momentum J=40, 50, 60 and 70. The gap between CS and CC probabilities are increasing as J increases which reveals that Coriolis coupling effects get more and more important with increasing of J for the title reaction. Moreover, the exact quantum wave calculations show that the thermal rate constants between 300 K and 1000 K for the title reaction shows a temperature independent behavior similar to the H + CH reaction, but the value of the rate constant for the H + SiH reaction is an order of magnitude larger than that of the H + CH reaction.
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Keywords:
- reaction probability /
- integral cross section /
- rate constant
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