Schuurman Michael S, Yarkony David R
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
J Chem Phys. 2007 Jan 28;126(4):044104. doi: 10.1063/1.2430718.
The existence of a seam of conical intersection, the reference seam, does not rule out the existence of additional disjoint seams of conical intersection. These disjoint seams intersect the g-h planes of the reference seam, a region usually assumed to be devoid of intersections, potentially leading to unexpected points of degeneracy in close proximity to the original conical intersection. Here the authors show how the locus of these disjoint seams can be predicted employing a Hamiltonian derived from second-order perturbation theory. Dramatic differences between the g-h planes of the reference and disjoint seams are found and are expected to have a profound impact on nuclear dynamics. Numerical studies of both high symmetry (D(3h), C(3)H(3)) and low symmetry (C(2v), C(2)H(2)N) species are presented.
锥形交叉缝（参考缝）的存在并不排除其他不相连的锥形交叉缝的存在。这些不相连的缝与参考缝的g-h平面相交，而该区域通常被认为不存在交叉，这可能会在原始锥形交叉附近导致意外的简并点。本文作者展示了如何利用由二阶微扰理论导出的哈密顿量来预测这些不相连缝的轨迹。研究发现参考缝和不相连缝的g-h平面之间存在显著差异，预计这将对核动力学产生深远影响。文中还给出了高对称性（D(3h)、C(3)H(3)）和低对称性（C(2v)、C(2)H(2)N）物种的数值研究结果。
