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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Role of Overlap between the Discrete State and Pseudocontinuum States in Stabilization Calculations of Metastable States
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Role of Overlap between the Discrete State and Pseudocontinuum States in Stabilization Calculations of Metastable States

机译：在稳定状态下离散状态和伪动脉素态之间的角色在稳定的状态下的作用

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摘要

In a diabatic picture metastable states subject to decay by electron detachment can be viewed as arising from the coupling between a discrete state and a continuum. In treating such states with bound-state quantum chemical methods, the continuum is discretized. In this study, we elucidate the role of overlap in this interaction in the application of the stabilization method to temporary anion states. This is accomplished by use of a minimalist stabilization calculation on the lowest energy l = 2 (D) resonance of the finite spherical well potential using two basis functions, one describing the diabatic discrete state and the other a diabatic discretized continuum state. We show that even such a simple treatment predicts a complex resonance energy in good agreement with the exact result. If the energy of the discrete state is assumed to be constant, which is tantamount to orthogonalizing the discretized continuum state to the discrete state, it is demonstrated that the square of the off-diagonal coupling has a maximum close to the crossing point of the orthogonalized diabatic curves and that the curvature in the coupling is responsible for the complex stationary point associated with the resonance. Moreover, this curvature is a consequence of the overlap between the two diabatic states.
机译：在一幅非绝热图片中，由于电子分离而衰变的亚稳态可以被看作是由离散态和连续态之间的耦合引起的。在用束缚态量子化学方法处理这些态时，连续介质是离散的。在这项研究中，我们阐明了在将稳定化方法应用于暂时阴离子状态时，重叠在这种相互作用中的作用。这是通过使用两个基函数（一个描述非绝热离散态，另一个描述非绝热离散连续态）对有限球阱势的最低能量l=2（D）共振进行最小稳定计算来实现的。我们发现，即使如此简单的处理也能预测复杂的共振能量，这与精确的结果非常一致。如果假设离散态的能量为常数，这相当于将离散连续态正交化为离散态，证明了非对角耦合的平方在正交非绝热曲线的交叉点附近有一个最大值，耦合中的曲率是与共振相关的复驻点的原因。此外，这种曲率是两种非绝热状态重叠的结果。

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