耦合集团理论中的交叉条件
Crossing conditions in coupled cluster theory
摘要：
我们推导出了耦合团簇理论中电子态在圆锥形交叉点处的交叉条件，并证明了如果耦合团簇雅可比矩阵是无亏损的，那么对于一个固有实（复）哈密顿量，两（三）个独立的条件被正确地放置在核自由度上.计算使用耦合簇理论在$2 {^{1}}A' / 3 {^{1}}A'$圆锥形交叉次氟酸说明非物理文物与缺陷在偶然的相同的对称交叉。特别是，所观察到的交叉缝折叠的空间的正确的维数，这表明，微小的修改的理论需要它提供一个正确的描述一般圆锥形交叉。我们发现，一个偶然的对称性允许$1 {^{1}}A" / 2 {^{1}}A"$交叉在硫化氢适当的描述，显示没有文物以及线性的能隙的一阶在分支平面。
英文摘要：
We derive the crossing conditions at conical intersections between electronic states in coupled cluster theory, and show that if the coupled cluster Jacobian matrix is nondefective, two (three) independent conditions are correctly placed on the nuclear degrees of freedom for an inherently real (complex) Hamiltonian. Calculations using coupled cluster theory on an $2 {^{1}}A' / 3 {^{1}}A'$ conical intersection in hypofluorous acid illustrate the nonphysical artifacts associated with defects at accidental same-symmetry intersections. In particular, the observed intersection seam is folded about a space of the correct dimensionality, indicating that minor modifications to the theory are required for it to provide a correct description of conical intersections in general. We find that an accidental symmetry allowed $1 {^{1}}A" / 2 {^{1}}A"$ intersection in hydrogen sulfide is properly described, showing no artifacts as well as linearity of the energy gap to first order in the branching plane.
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