Panda Aditya Narayan, Sathyamurthy N
Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India.
J Chem Phys. 2004 Nov 15;121(19):9343-51. doi: 10.1063/1.1797711.
A global analytical potential energy surface for the ground state of H(3)(-) has been constructed by fitting an analytic function to the ab initio potential energy values computed using coupled cluster singles and doubles with perturbative triples [CCSD(T)] method and Dunning's augmented correlation consistent polarized valence triple zeta basis set. Using this potential energy surface, time-dependent quantum mechanical wave packet calculations were carried out to calculate the reaction probabilities (P(R)) for the exchange reaction H(-)+H(2)(v, j)-->H(2)+H(-), for different initial vibrational (v) and rotational (j) states of H(2), for total angular momentum equal to zero. With increase in v, the number of oscillations in the P(R)(E) plot increases and the oscillations become more pronounced. While P(R) increases with increase in rotational excitation from j=0 to 1, it decreases with further increase in j to 2 over a wide range of energies. In addition, rotational excitation quenches the oscillations in P(R)(E) plots.
通过将一个解析函数拟合到使用耦合簇单双激发并包含微扰三激发[CCSD(T)]方法以及邓宁增强相关一致极化价三ζ基组计算得到的从头算势能值，构建了H(3)(-)基态的全局分析势能面。利用该势能面，进行了含时量子力学波包计算，以计算在总角动量等于零的情况下，对于H(2)不同的初始振动(v)和转动(j)状态，交换反应H(-)+H(2)(v, j)-->H(2)+H(-)的反应概率(P(R))。随着v的增加，P(R)(E)图中的振荡次数增加且振荡变得更加明显。虽然P(R)随着转动激发从j = 0增加到1而增加，但在很宽的能量范围内，随着j进一步增加到2它会减小。此外，转动激发会抑制P(R)(E)图中的振荡。
