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首页> 外文期刊>The Journal of Chemical Physics >SELECTIVE PRODUCTION OF PHOTOFRAGMENTS BY MONITORING THE SHAPE OF ASYMMETRIC RESONANCES IN OH PHOTODISSOCIATION - DEPENDENCE ON INITIAL VIBRATIONAL STATES
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SELECTIVE PRODUCTION OF PHOTOFRAGMENTS BY MONITORING THE SHAPE OF ASYMMETRIC RESONANCES IN OH PHOTODISSOCIATION - DEPENDENCE ON INITIAL VIBRATIONAL STATES

机译：通过监测OH光解离中不对称共振的形状来选择性生产光片段-取决于初始振动状态

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摘要

Quantum mechanical analysis is presented on the vibrational state dependence of the total dissociation cross sections and the branching ratios of O(P-3(j), j=0,1,2) in the predissociation of OH. Two transformation matrices, each of which describes the relation between an atomic term limit and the correlating molecular states, are constructed and incorporated in the close coupling calculations. The branching ratios of O(P-3(j), j=0,1,2) depend very sensitively on the vibrational levels (upsilon=0-4) of the initial X (2) Pi state. The variations of the spin-orbit distributions as a function of the excitation energy near the asymmetric resonances change markedly depending on the vibrational levels. The variations are either redshifted or blueshifted from the resonance position, depending on the degree of asymmetry of the resonances. The widths of the variations tend to increase with increasing vibrational quantum number of the initial state, suggesting the possibility of choosing the proper linewidths in the experiments to selectively produce the photofragments in one-photon process. Discussion is presented on the applicability of the theoretical scheme to analyze the recent measurements by Neumark and co-workers [J. Chem. Phys. 103, 2495 (1995)] on the product fine structure distributions in the predissociation of O-2. (C) 1996 American Institute of Physics. [References: 39]
机译：对总解离截面的振动状态依赖性以及OH在预分解中O（P-3（j），j = 0,1,2）的支化率进行了量子力学分析。构造了两个变换矩阵，每个变换矩阵描述了原子项极限与相关分子状态之间的关系，并将其合并到紧密耦合计算中。 O（P-3（j），j = 0,1,2）的分支比非常敏感地取决于初始X（2）Pi状态的振动水平（upsilon = 0-4）。在不对称共振附近，自旋轨道分布的变化是激发能量的函数，其变化取决于振动水平。取决于共振的不对称程度，这些变化从共振位置是红移或蓝移。变化的宽度倾向于随着初始状态的振动量子数的增加而增加，这表明有可能在实验中选择适当的线宽以在单光子过程中选择性地产生光碎片。讨论了该理论方案是否适用于分析Neumark和他的同事们最近的测量[J．化学物理103，2495（1995）]关于O-2的预离解中产物的精细结构分布。 （C）1996年美国物理研究所。 [参考：39]

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