The rate constants for the H+H2 reaction and its isotopic analogs at low temperatures: Wigner threshold law behavior
The rate constants for the H+H2 reaction and its isotopic analogs at low temperatures: Wigner threshold law behavior
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H H2 反应及其同位素类似物在低温下的速率常数：维格纳阈值定律行为
DOI：
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发表时间：
1987
期刊：
影响因子：
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通讯作者：
G. Schatz
中科院分区：
文献类型：
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作者：
T. Takayanagi;N. Masaki;K. Nakamura;M. Okamoto;S. Sato;G. Schatz
使用 LSTH 势面计算了极低温度下 H+H2 反应及其同位素类似物的变分过渡态理论速率常数。研究发现，维格纳阈值定律在数量上保持在 1 K 以下，在 5 K 时平均保持在 34% 以内。如果在计算传输系数时使用具有正确阈值行为的隧道概率，则过渡态理论速率常数与维格纳阈值定律的要求一致。利用这些计算出的速率常数，估算了固体 H2、D2 和 HD 中 H 和 D 原子的衰变速率，并与实验进行了比较。所发现的良好一致性表明这些衰变是通过量子力学隧道交换反应发生的。
Variational transition‐state theory rate constants for the H+H2 reaction and its isotopic analogs at very low temperatures have been calculated using the LSTH potential surface. The Wigner threshold law is found to hold quantitatively below 1 K and to within 34% on average at 5 K. The transition‐state theory rate constants are found to be consistent with the requirements of the Wigner threshold law provided that a tunneling probability having the correct threshold behavior is used in calculating the transmission coefficient. Using these calculated rate constants, decay rates of H and D atoms in solid H2, D2, and HD were estimated and compared with experiment. The good agreement found suggests that these decays occur through quantum mechanical tunneling exchange reactions.