Hochlaf M, Taylor S, Eland J H D
Theoretical Chemistry Group, University of Marne-La-Vallée, Champs Sur Marne, F-77454, Marne-La-Vallée, Cedex 2, France.
J Chem Phys. 2006 Dec 7;125(21):214301. doi: 10.1063/1.2400029.
Highly correlated ab initio methods have been used to generate one-dimensional cuts of the six-dimensional potential energy surfaces of the quartet and lowest doublet states for the HCCH(+) ion along the CH, CC, and cis and trans bending coordinates. Transition dipole moments and spin-orbit matrix elements are deduced. For the lowest 1 (4)Sigma(u) (+) state, the calculations predict a possible photon emission through the 1 (4)Pi(g)<--1 (4)Sigma(u) (+) transition competing with internal conversion and predissociation processes. The potential surfaces are used together with spin-orbit matrix elements to discuss the metastability and the predissociation processes forming the C(2)HC(2)H(+)+H(+)H products. Multistep spin-orbit induced predissociation pathways are suggested.
高度相关的从头算方法已被用于生成HCCH(+)离子四重态和最低二重态的六维势能面沿CH、CC以及顺式和反式弯曲坐标的一维截面。推导了跃迁偶极矩和自旋轨道矩阵元。对于最低的1(4)Σ(u)(+)态，计算预测通过1(4)Π(g)←1(4)Σ(u)(+)跃迁可能存在光子发射，该发射与内转换和预解离过程相互竞争。势能面与自旋轨道矩阵元一起用于讨论亚稳性以及形成C(2)HC(2)H(+)+H(+)H产物的预解离过程。提出了多步自旋轨道诱导的预解离途径。
