Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, India.
J Chem Phys. 2011 Nov 21;135(19):194302. doi: 10.1063/1.3660222.
A systematic study of the reagent ro-vibrational excitations in H(2) + OH reaction is presented on three different potential energy surfaces using the multiconfiguration time-dependent Hartree method. An exact form of the kinetic energy operator including Coriolis coupling has been used. Coupled channel results on WDSE surface for vibrational excitation of H(2) produce very large cross sections in accordance with the previous approximate results. The rate constant obtained for H(2)(v = 1) at 300 K on the YZCL2 surface shows an excellent agreement with the most recent experimental result. Quantum dynamical results for ro-vibrational excitation of reagents obtained on the WSLFH surface show similar behavior to previous quasiclassical trajectory studies. The integral cross sections obtained for excited reagent rotations exhibit contrasting trends on the three surfaces. The effects are explained considering the different orientations of the transition state structure and the individual surface characteristics.
采用多组态含时Hartree 方法在三个不同的势能面上对 H(2) + OH 反应中试剂的 ro-振动激发进行了系统研究。使用了包含科里奥利耦合的精确动能算子形式。对于 H(2)振动激发的 WDSE 表面的耦合通道结果与先前的近似结果一致，产生了非常大的截面。在 YZCL2 表面上，300 K 时 H(2)(v = 1)的速率常数与最近的实验结果非常吻合。在 WSLFH 表面上获得的试剂 ro-振动激发的量子动力学结果表现出与先前准经典轨迹研究相似的行为。在三个表面上，激发试剂旋转的积分截面表现出相反的趋势。考虑到过渡态结构的不同取向和各个表面的特性，可以解释这些影响。
