Topology and dynamics of vibronically coupled potential energy surfaces : general aspects and application to the ozone cation
Topology and dynamics of vibronically coupled potential energy surfaces : general aspects and application to the ozone cation
复制标题
振动耦合势能面的拓扑和动力学：一般方面和在臭氧阳离子中的应用
DOI：
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
L. Cederbaum
中科院分区：
文献类型：
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作者：
H. Müller;H. Köppel;L. Cederbaum
本文提出并讨论了一种多模电子振动耦合哈密顿量，它在核位移中包含了二阶耦合项。详细分析了绝热势能面的驻点和多维圆锥相交点。二次耦合在不对称扭曲的核几何形状中产生多达三个固定点。对于两个完全对称的振动模式，圆锥交点的轨迹在完全对称坐标空间中形成椭圆或双曲线。如果双线性电子振动耦合项是实质性的，则在非对称畸变核框架处可能出现新的锥形交叉
A multi-mode vibronic coupling Hamiltonian is presented and discussed which includes coupling terms up to second order in the nuclear displacements. The stationary points of and the multidimensional conical intersections between the associated adiabatic potential energy surfaces are analyzed in some detail. Quadratic coupling gives rise to up to three stationary points at asymmetrically distorted nuclear geometries. For two totally symmetric vibrational modes the loci of the conical intersections form ellipses or hyperbolas in the space of the totally symmetric coordinates. If bilinear vibronic coupling terms are substantial new conical intersections at an asymmetrically distorted nuclear framework may arise