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首页> 外文期刊>The Journal of Chemical Physics >QUANTUM PHASE SPACE THEORY FOR THE CALCULATION OF V-CENTER-DOT-J VECTOR CORRELATIONS
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QUANTUM PHASE SPACE THEORY FOR THE CALCULATION OF V-CENTER-DOT-J VECTOR CORRELATIONS

机译：计算V-CENTER-DOT-J向量相关性的量子相空间理论

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The quantum state-counting phase space theory commonly used to describe ''barrierless'' dissociation is recast in a helicity basis to calculate photofragment v . j correlations. Counting pairs of fragment states with specific angular momentum projection numbers on the relative velocity provides a simple connection between angular momentum conservation and the v . j correlation, which is not so evident in the conventional basis for phase space state counts. The upper bound on the orbital angular momentum, I, imposed by the centrifugal barrier cannot be included simply in the helicity basis, where I is not a good quantum number. Two approaches for an exact calculation of the v . j correlation including the centrifugal barrier are described to address this point, although the simpler helicity state count with no centrifugal barrier correction is remarkably good in many cases. An application to the photodissociation of NCCN is consistent with recent classical phase space calculations of Klippenstein and Cline. The experimentally observed vector correlation exceeds the phase space theory prediction. We take this as evidence of incomplete mixing of the K states of the linear parent molecule at the transition state, corresponding to an evolution of the body-fixed projection number K into the total helicity of the fragment pair state. The average over a thermal distribution of parent angular momentum in the special case of a linear molecule does not significantly reduce the v . j correlation below that computed for total J=0. Predictions of the v . j correlations for the unimolecular dissociation of NCNO and CH2CO are also provided. (C) 1996 American Institute of Physics. [References: 44]
机译：通常在描述螺旋度的基础上重塑通常用于描述“无障碍”解离的量子状态计数相空间理论，以计算光碎度v。 j相关。对相对速度上具有特定角动量投影数的碎片状态对进行计数，就可以在角动量守恒和v之间建立简单的联系。 j相关，在相空间状态计数的传统基础上不是很明显。离心势垒所施加的轨道角动量I的上限不能简单地包含在螺旋度基础中，因为I不是一个好的量子数。精确计算v的两种方法。尽管在许多情况下，没有离心势垒校正的简单螺旋状态计数非常好，但是描述了包括离心势垒的j相关性可以解决这一问题。 NCCN光解离的应用与Klippenstein和Cline的最新经典相空间计算是一致的。实验观察到的矢量相关性超出了相空间理论的预测。我们以此为证据，认为线性母体分子的K状态在过渡状态下不完全混合，这对应于固定的投影数K演变为片段对状态的总螺旋度。在线性分子的特殊情况下，母体角动量在热分布上的平均值不会显着降低v。 j相关性低于为总J = 0计算的相关性。 v的预测。还提供了NCNO和CH2CO单分子解离的相关性。 （C）1996年美国物理研究所。 [参考：44]

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