Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
J Comput Chem. 2011 Jun;32(8):1694-702. doi: 10.1002/jcc.21751. Epub 2011 Mar 1.
New ab initio potential energy surfaces for the ground (X̃1A') and excited (Ã1A″) electronic states of HSiCl were obtained by using the single and double excitation coupled-cluster theory with a noniterative perturbation treatment of triple excitations and the multi-reference configuration interaction with Davidson correction, respectively, employing an augmented correlation-consistent polarized valence quadruple zeta basis set. For the excited state Ã1A″, an extended active space (18 electrons in 12 orbitals) was used. The calculated vibrational energy levels of HSiCl and DSiCl of the ground and excited electronic states are in better agreement with the available experimental values than the previous theoretical results. In addition, with the calculated transition dipole moment, the absorption and emission spectra of HSiCl and DSiCl were calculated using an efficient single Lanczos propagation method and are in reasonable agreement with the available observed spectra.
通过使用单激发和双激发耦合簇理论，分别采用非迭代的三激发微扰处理和多参考组态相互作用与戴维森修正，使用扩充相关一致极化价四元zeta 基组，获得了 HSiCl 的基态 (X̃1A') 和激发态 (Ã1A″) 的从头算势能面。对于激发态 Ã1A″，使用了扩展的活性空间（12 个轨道中的 18 个电子）。与以前的理论结果相比，计算得到的 HSiCl 和 DSiCl 的基态和激发态的振动能级与可用的实验值更吻合。此外，利用计算得到的跃迁偶极矩，采用有效的单 Lanczos 传播方法计算了 HSiCl 和 DSiCl 的吸收和发射光谱，并与可用的观察光谱吻合良好。
