Conical intersections of three states: Energies, derivative couplings, and the geometric phase effect in the neighborhood of degeneracy subspaces. Application to the allyl radical
Conical intersections of three states: Energies, derivative couplings, and the geometric phase effect in the neighborhood of degeneracy subspaces. Application to the allyl radical
复制标题
三种状态的圆锥相交：能量、导数耦合以及简并子空间邻域中的几何相位效应。
DOI：
10.1063/1.1623483
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发表时间：
2003
影响因子：
4.4
通讯作者：
D. Yarkony
中科院分区：
文献类型：
--
作者：
Seungsuk Han;D. Yarkony
考虑相同对称性的三个状态（表示为i，j，k）的圆锥交点的五维分支空间的性质。将微扰模型的结果与烯丙基自由基的三种光谱观察状态的多参考构型相互作用计算进行比较。特别令人感兴趣的是分支空间的三维子空间，其中两个状态保持简并。研究了简并子空间附近的能量、导数耦合和几何相位效应。简并子空间包括两种圆锥交点，i,j 和 j,k。三态交叉的存在会影响穿过闭环的波函数（和导数耦合）的相位。例如，在分支空间中，如果闭环包含三态交点，则限制闭环的表面中的圆锥交点的数量和种类。
The properties of the five-dimensional branching space of conical intersections of three states of the same symmetry (denoted i,j,k) are considered. The results of a perturbative model are compared with multireference configuration interaction calculations for three spectroscopically observed states of the allyl radical. Of particular interest is the three-dimensional subspace of the branching space where two states remain degenerate. The energies, derivative couplings and geometric phase effect are studied in the neighborhood of this degeneracy subspace. The degeneracy subspace includes two kinds of conical intersections, i,j and j,k. The existence of a three-state intersection impacts the phase of the wave functions (and the derivative coupling) traversing a closed loop. For example, in the branching space, the number and kind of conical intersections in a surface bounding the closed loop is constrained if the closed loop contains the three-state intersection.