Intramolecular dynamics by photoelectron spectroscopy. II. Nonadiabatic processes.
Intramolecular dynamics by photoelectron spectroscopy. II. Nonadiabatic processes.
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通过光电子能谱研究分子内动力学。
DOI：
10.1063/1.446292
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发表时间：
1983
影响因子：
4.4
通讯作者：
M. Hubin
中科院分区：
文献类型：
--
作者：
D. Dehareng;B. Leyh;M. Desouter;J. Lorquet;J. Delwiche;M. Hubin
电子谱的傅立叶变换产生自相关函数，该函数提供有关波包在跃迁中达到的电子态的势能表面上的传播的信息。即使存在非绝热相互作用，即当波包在与一个部分分支到另一个势能表面的特定表面交叉时，该公式也是有效的。对于与连续体相互作用的多个离散状态的模型，给出了相关函数的显式表达式。在一次和两次共振的情况下给出了封闭式解。还导出了一个在强耦合极限下有效的非常简单的公式。该方法应用于HBr+的A 2Σ+态光电子能谱，结果表明其对应于强耦合情况。
The Fourier transform of an electronic spectrum leads to an autocorrelation function which provides information on the propagation of a wave packet on the potential energy surface of the electronic state reached in the transition. The formula is valid even when nonadiabatic interaction is present, i.e., when the wave packet splits at a particular surface crossing with one part branching off to another potential energy surface. An explicit expression of the correlation function is given for a model of several discrete states interacting with a continuum. Closed‐form solutions are given in the case of one and two resonances. A very simple formula valid in the strong coupling limit is also derived. The method is applied to the photoelectron spectrum of state A 2Σ+ of HBr+, which is shown to correspond to the strong coupling case.