Schuurman Michael S, Weinberg Daniel E, Yarkony David R
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
J Chem Phys. 2007 Sep 14;127(10):104309. doi: 10.1063/1.2764052.
A method to simulate photoelectron spectra for states coupled by conical intersections and the spin-orbit interaction is reported. The algorithm is based on the multimode vibronic coupling model and treats the spin-orbit interaction in a nonperturbative manner. Since the algorithm is not dependent on molecular symmetry, the approach is generally applicable to accidental conical intersections as well as the symmetry required intersections found in Jahn-Teller molecules. The method is also computationally efficient using energy gradient and derivative coupling information to limit the number of nuclear configurations at which ab initio data are required. This approach is applied to simulate the negative ion photoelectron spectrum of the methylthio radical. The two-state Hamiltonian employed to describe this system was determined employing ab initio gradients and derivative couplings at only 17 nuclear configurations.
报道了一种用于模拟由锥形交叉和自旋 - 轨道相互作用耦合的态的光电子能谱的方法。该算法基于多模振子 - 电子耦合模型，并以非微扰方式处理自旋 - 轨道相互作用。由于该算法不依赖于分子对称性，该方法通常适用于偶然的锥形交叉以及在 Jahn - Teller 分子中发现的对称性所需的交叉。该方法还利用能量梯度和导数耦合信息来限制需要从头算数据的核构型数量，从而在计算上是高效的。该方法被应用于模拟甲硫基自由基的负离子光电子能谱。用于描述该系统的双态哈密顿量仅通过在 17 个核构型处的从头算梯度和导数耦合来确定。
