On the consequences of nonremovable derivative couplings. I. The geometric phase and quasidiabatic states: A numerical study
On the consequences of nonremovable derivative couplings. I. The geometric phase and quasidiabatic states: A numerical study
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关于不可拆卸导数耦合的后果。
DOI：
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
D. Yarkony
中科院分区：
文献类型：
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作者：
D. Yarkony
圆锥相交通过几何相位效应和导数耦合中的奇异性使绝热态基础上的核动力学计算处理复杂化。非绝热表象试图消除这些困难。然而，在多原子分子中，绝热态到非绝热态的转变必然是近似的，因为导数耦合不能被严格地去除。在构造近似非绝热态时很少考虑这一点。通过考虑H3中1 2A′-2 2A′圆锥相交缝附近导数耦合沿着闭合回路的积分，研究了导数耦合的不可去除部分.
Conical intersections complicate the computational treatment of nuclear dynamics in the adiabatic state basis through the geometric phase effect and singularities in the derivative couplings. The diabatic representation seeks to eliminate these difficulties. However, the adiabatic to diabatic state transformation is necessarily approximate in a polyatomic molecule since the derivative couplings cannot be rigorously removed. This point is rarely considered when constructing approximate diabatic states. The nonremovable part of the derivative couplings is investigated by considering the integral of the derivative coupling along closed loops in the vicinity of the 1 2A′–2 2A′ seam of conical intersections in H3.