Multistate vibronic interactions in the benzene radical cation.: I.: Electronic structure calculations
Multistate vibronic interactions in the benzene radical cation.: I.: Electronic structure calculations
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DOI：
10.1063/1.1491397
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发表时间：
2002-08-08
影响因子：
4.4
通讯作者：
Szalay, PG
中科院分区：
文献类型：
--
作者：
Döscher, M;Köppel, H;Szalay, PG
在线性振动耦合方案的框架下，从理论上研究了苯自由基阳离子中的多态振动相互作用。在处理中包括最低的五个电子态；考虑到一些态的简并，这相当于八个耦合势能面。对系统参数进行了不同类型的从头计算，发现它们相互吻合，从而相互支持。计算揭示了不同状态的势能面之间的低能锥形相交的完整序列。指出了它们对这一典型的有机自由基阳离子的核动力学的重要性。这些耦合势能面的波包动力学模拟将在下一篇论文(论文II)中给出。(C)2002年美国物理研究所。
The multistate vibronic interactions in the benzene radical cation are investigated theoretically, employing the framework of a linear vibronic coupling scheme. The five lowest electronic states are included in the treatment; in view of the degeneracy of some states, this amounts to eight coupled potential energy surfaces. Different types of ab initio calculations have been performed for the system parameters and been found to be in good mutual agreement, thus supporting each other. The calculations reveal a whole sequence of low-energy conical intersections between the potential energy surfaces of different states. Their importance for the nuclear dynamics in this prototypical organic radical cation is pointed out. Wave-packet dynamical simulations for these coupled potential energy surfaces will be presented in the following paper (Paper II). (C) 2002 American Institute of Physics.