Classical trajectory study of product state vector correlations: A model for the photodissociation of CF3NO
Classical trajectory study of product state vector correlations: A model for the photodissociation of CF3NO
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产物状态向量相关性的经典轨迹研究：CF3NO 光解离模型
DOI：
10.1063/1.474818
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发表时间：
1997
影响因子：
4.4
通讯作者：
J. I. Cline
中科院分区：
文献类型：
--
作者：
K. Fukui;J. H. Frederick;J. I. Cline
CF3NO 的光解动力学通过 S0 和 T1 电子势表面上的三维经典轨迹计算进行建模，其中包括所有振动和旋转自由度。 CF3NO 的分子内势能面是通过优化分析势函数中的参数来获得的，以最好地拟合光谱数据和 UMP2/6-31+G* 水平从头计算的结果。使用模拟分子束实验条件的新方法计算初始母分子能量和角动量分布。计算旨在解释亚硝基烷烃光解中相关 NO 产物状态分布的实验测量结果。结果表明，NO光碎片的v-j相关性主要由T1表面上的C-N-O弯曲力常数和出口通道势垒决定。
The photodissociation dynamics of CF3NO are modeled by three-dimensional classical trajectory calculations on the S0 and T1 electronic potential surfaces that include all vibrational and rotational degrees of freedom. The intramolecular potential energy surface for CF3NO was obtained by optimizing parameters in an analytical potential function to best fit spectroscopic data and the results of UMP2/6-31+G* level ab initio calculations. Initial parent molecule energy and angular momentum distributions are computed using a new method that simulates the conditions of molecular beam experiments. The calculations are directed at interpreting experimental measurements of correlated NO product state distributions in the photodissociation of the nitrosoalkanes. The results show that the v–j correlation of NO photofragment is primarily determined by the C–N–O bending force constant and exit channel barrier on the T1 surface.