A Calculation of the Rates of the Ortho‐Para Conversions and Isotope Exchanges in Hydrogen
A Calculation of the Rates of the Ortho‐Para Conversions and Isotope Exchanges in Hydrogen
复制标题
氢中邻位转化率和同位素交换率的计算
DOI：
10.1063/1.1730599
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发表时间：
1959
期刊：
影响因子：
--
通讯作者：
I. Shavitt
中科院分区：
文献类型：
--
作者：
I. Shavitt
H+H2→H2+H类型的各种基元反应的速率，包括邻-帕拉转化或同位素交换，已经通过绝对反应速率理论计算，使用H3能量表面形状的新的基本量子力学数据，但估计活化能以拟合实验结果。过渡复合物是线性和对称的，与半经验表面的非对称复合物形成对比，导致计算中的一些定性和定量差异。隧道效应的修正是精确计算的，假设势垒是Eckart型。不同作者获得的实验结果之间的差异和他们的数据中可能的不准确性使得很难评估计算的速率常数的准确性。
The rates of the various elementary reactions of the type H+H2→H2+H, involving ortho‐para conversions or isotope exchanges, have been calculated by the absolute reaction rate theory, using new fundamental quantum‐mechanical data for the shape of the H3 energy surface, but estimating the activation energy to fit experimental results. The transition complex is linear and symmetric, in contrast with the asymmetric complex of the semiempirical surface, resulting in some qualitative, as well as quantitative, differences in the calculation. The tunnel effect correction is computed exactly, on the assumption that the potential barrier is of the Eckart type. The disparity between the experimental results obtained by different authors and the probable inaccuracies in their data make it very difficult to assess the accuracy of the calculated rate constants.