Amaran Saieswari, Kumar Sanjay
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India.
J Chem Phys. 2008 Mar 28;128(12):124306. doi: 10.1063/1.2894311.
State-resolved differential cross section, integral cross section, average vibrational energy transfer, and the relative transition probability are computed for the H(+)+NO system using our newly obtained ab initio potential energy surfaces (PES) at the multireference configuration interaction level of accuracy employing the correlation consistent polarized valence triple zeta basis set. The quantum dynamics is treated within the vibrational close-coupling rotational infinite-order sudden approximation using the coupled ground state and first excited state ab initio quasidiabatic PES. The computed collision attributes for the inelastic vibrational excitation are compared with the state-to-state scattering data available at E(c.m.)=9.5 eV and E(c.m.)=29.03 eV and are found to be in overall good agreement with those of the experiments. The results for the vibrational charge transfer processes at these collision energies are also presented.
利用我们新获得的多参考组态相互作用精度水平下的从头算势能面(PES),采用相关一致极化价三重ζ基组,计算了H(+)+NO体系的态分辨微分截面、积分截面、平均振动能量转移和相对跃迁概率。量子动力学在振动密耦合转动无穷阶突然近似下处理,使用耦合基态和第一激发态从头算准绝热PES。将计算得到的非弹性振动激发碰撞属性与质心能量E(c.m.) = 9.5 eV和E(c.m.) = 29.03 eV下的态-态散射数据进行比较,发现与实验结果总体吻合良好。还给出了这些碰撞能量下振动电荷转移过程的结果。