Effects of higher order Jahn-Teller coupling on the nuclear dynamics.
Effects of higher order Jahn-Teller coupling on the nuclear dynamics.
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高阶 Jahn-Teller 耦合对核动力学的影响。
DOI：
10.1063/1.1646371
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
W. Eisfeld
中科院分区：
文献类型：
--
作者：
A. Viel;W. Eisfeld
本文研究了高阶Jahn-Teller耦合项对非绝热动力学的影响。特别令人感兴趣的是，当退化状态的势能面表现出明显的非谐性的情况下。为了证明这种效应，我们以NO（3）的光敏（2）E（'）态的e（'）伸缩振动为基础，对二维E乘符号的e Jahn-Teller模型系统进行了实际的例子处理。在非绝热表象中导出了六阶E乘圆符号的Jahn-Teller哈密顿量，该哈密顿量对任何具有C（3）旋转轴的系统都是有效的.这diabatization计划相比，低阶扬-泰勒哈密顿和对称性适应以及特设近似。低阶势导致动力学中明显的定量和定性差异，包括平均值、自相关函数（以及相应的光谱）和电子布居演化的差异。在所处理的具体例子中，四阶和五阶势的结果与六阶参考系非常相似。相比之下，近似的六阶哈密顿，虽然相应的绝热表面似乎是几乎相同的，结果在显着的差异。本文简要讨论了高维现实系统动力学的可能后果。
In this paper effects of higher order Jahn-Teller coupling terms on the nonadiabatic dynamics are studied. Of particular interest is the case when the potential energy surfaces of the degenerate state show pronounced anharmonicity. In order to demonstrate the effects a two-dimensional E multiply sign in circle e Jahn-Teller model system is treated which is based on the e(') stretching vibration of the photoactive (2)E(') state of NO(3) as a realistic example. The sixth order E multiply sign in circle e Jahn-Teller Hamiltonian is derived in the diabatic representation which is valid for any system with a C(3) rotation axis. This diabatization scheme is compared to lower-order Jahn-Teller Hamiltonians and to symmetry adapted as well as ad hoc approximations. Lower-order potentials result in pronounced quantitative and qualitative differences in the dynamics, including differences in the evolution of mean values, the autocorrelation functions (and thus the corresponding spectra), and the electronic population evolution. In the particular example treated, the results of fourth and fifth order potentials are very similar to the sixth order reference system. In contrast, the approximate sixth order Hamiltonians, though the corresponding adiabatic surfaces seem to be nearly identical, results in pronounced differences. The possible consequences for the dynamics of realistic systems with higher dimensionality are briefly discussed.