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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation of CH3I: A full-dimensional (9D) quantum dynamics study
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Photodissociation of CH3I: A full-dimensional (9D) quantum dynamics study

机译：CH3I的光解离：全方位（9D）量子动力学研究

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摘要

The photodissociation of methyl iodide in the A band is studied by full-dimensional (9D) wave packet dynamics calculations using the multiconfigurational time-dependent Hartree approach. The potential energy surfaces employed are based on the diabatic potentials of Xie et al. [J. Phys. Chem. A 2000, 104, 1009] and the vertical excitation energy is taken from recent ab initio calculations [Alekseyev et al. J. Chem. Phys. 2007, 126, 234102]. The absorption spectrum calculated for exclusively parallel excitation agrees well with the experimental spectrum of the A band. The electronic population dynamics is found to be strongly dependent on themotion in the torsional coordinate related to the H_3-C-I bend, which presumably is an artifact of the diabatic model employed. The calculated fully product state-selected partial spectra can be interpreted based on the reflection principle and suggests strong coupling between the C-I stretching and the H_3-C-I bending motions during the dissociation process. The computed rotational and vibrational product distributions typically reproduce the trends seen in the experiment. In agreement with experiment, a small but significant excitation of the total symmetric stretching and the asymmetric bending modes of the methyl fragment can be seen. In contrast, the umbrella mode of the methyl is found to be too highly excited in the calculated distributions.
机译：通过使用多配置时变Hartree方法进行全尺寸（9D）波包动力学计算，研究了A波段甲基碘的光解离。所使用的势能面基于谢等人的绝热势。 [J.物理化学A 2000、104、1009]和垂直激励能量取自最近的从头算起[Alekseyev等。 J.化学物理2007，126，234102]。专门为平行激发计算的吸收光谱与A波段的实验光谱非常吻合。发现电子种群动力学很大程度上取决于与H_3-C-I弯曲有关的扭转坐标中的运动，这可能是所采用的绝热模型的伪影。可以基于反射原理来解释所计算出的全产品状态选择的部分光谱，并表明在解离过程中C-1拉伸与H_3-C-1弯曲运动之间存在强耦合。计算得出的旋转和振动产品分布通常会再现实验中看到的趋势。与实验相一致，可以看到甲基片段的总对称拉伸和不对称弯曲模式的微小但显着的激发。相反，在计算的分布中发现甲基的伞形模态太高了。

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