Department of Physics, Stockholm University, AlbaNova University Center, S-106 91 Stockholm, Sweden.
Department of Physics and Astronomy, Drake University, Des Moines, Iowa 50311, USA.
J Chem Phys. 2017 Aug 28;147(8):084304. doi: 10.1063/1.5000266.
The dissociative recombination of HCl, including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0, to the first three excited vibrational states, v = 1, v = 2, and v = 3, are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.
研究了 HCl 的离解复合，包括直接机制和间接机制。对于直接过程，通过将电子散射计算与离子和里德堡态的多参考组态相互作用计算相结合，来计算相关的电子态，以获得共振位置和自电离宽度。通过求解含时薛定谔方程，计算了沿电子共振态的直接离解截面。对于间接过程，在离化阈值以上的能量处，通过散射矩阵元素的振动框架变换，得到截面的上限值。考虑了离子核从基态振动能级 v=0 到第一、第二和第三激发振动能级 v=1、v=2 和 v=3 的振动激发。忽略了自电离，并考虑了离子势能的自旋轨道劈裂对间接离解复合截面的影响。将计算出的截面与测量值进行了比较。
