Unified Description of the Jahn–Teller Effect in Molecules with Only C s Symmetry: Cyclohexoxy in Its Full 48-Dimensional Internal Coordinates
Unified Description of the Jahn–Teller Effect in Molecules with Only C s Symmetry: Cyclohexoxy in Its Full 48-Dimensional Internal Coordinates
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仅具有 C s 对称性的分子中 Jahn-Teller 效应的统一描述：全 48 维内坐标中的环己氧基
DOI：
10.1021/acs.jpca.1c09123
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Yarkony, David R.
中科院分区：
文献类型：
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作者：
Shen, Yifan;Yarkony, David R.
在全48维内坐标空间中，利用前馈神经网络拟合非绝热势能矩阵，确定了环己氧基的两个最低势能面，它们通过锥交点和自旋轨道相互作用耦合.电子结构数据在多参考组态相互作用与单，双激发水平。这些耦合表面和那些的烷氧基甲氧基和异丙氧基之间的基本平行建立。Dillon和Yarkony的早期工作得到了扩展。虽然使用Jahn-Teller有源模式的概念来理解这些相似之处是具有挑战性的，但它们很容易在以圆锥交叉点为中心的两个内部模式中看到：g能量差梯度矢量和h状态间耦合梯度矢量。换句话说，gandh矢量提供了一个统一的描述Jahn-Teller效应的分子表现出C3 v和准C3 v对称性。在全48振动内坐标空间的光谱模拟报告。这一频谱是使用最近开发的算法，旨在增加系统的大小，可以处理与时间无关的振动耦合方法。
The two lowest potential energy surfaces of cyclohexoxy which are coupled by conical intersections and the spin–orbit interaction are determined in the full 48-dimensional internal coordinate space using a feedforward neural network to fit a diabatic potential energy matrix. The electronic structure data are obtained at the multireference configuration interaction with single- and double-excitation level. Underlying parallels between these coupled surfaces and those of the alkoxy radicals methoxy and isopropoxy are established. Earlier work by Dillon and Yarkony is extended. While the parallels would have been challenging to appreciate using the concept of the Jahn–Teller active modes, they are readily seen in terms of two internal modes centered at the conical intersection:gthe energy difference gradient vector andhthe interstate coupling gradient vector. In other words,gandhvectors provide a unified description of the Jahn–Teller effect in molecules exhibiting C3v and quasi-C3v symmetries. A spectral simulation in the full 48-vibrational-internal coordinate space is reported. This spectrum is obtained using recently developed algorithms designed to increase the size of the systems that can be treated with a time-independent vibronic coupling approach.