Science. 1992 Jul 24;257(5069):519-22. doi: 10.1126/science.257.5069.519.
A fully quantal wavepacket approach to reactive scattering in which the best available H(3) potential energy surface was used enabled a comparison with experimentally determined rates for the D + H(2)(v = 1, j = 1) --> HD(v' = 0, 1, 2; j') + H reaction at significantly higher total energies (1.4 to 2.25 electron volts) than previously possible. The theoretical results are obtained over a sufficient range of conditions that a detailed simulation of the experiment was possible, thus making this a definitive comparison of experiment and theory. Good to excellent agreement is found for the vibrational branching ratios and for the rotational distributions within each product vibrational level. However, the calculated rotational distributions are slightly hotter than the experimentally measured ones. This small discrepancy is more marked for products for which a larger fraction of the total energy appears in translation. The most likely explanation for this behavior is that refinements are needed in the potential energy surface.
采用全量子波包方法研究反应散射，其中使用了最佳的 H(3)势能面，使我们能够将实验确定的 D+H(2)(v=1，j=1)→HD(v'=0，1，2；j')+H 反应速率与之前不可能达到的更高总能量（1.4 至 2.25 电子伏特）进行比较。理论结果是在足够的条件范围内获得的，因此可以对实验进行详细的模拟，从而实现实验和理论的明确比较。在每个产物振动能级内，振动分支比和转动分布都得到了很好的一致。然而，计算出的转动分布比实验测量的稍微热一些。对于那些总能量中有更大一部分出现在平动中的产物，这种小差异更为明显。这种行为的最可能解释是需要对势能面进行细化。
