Symmetries of activated complexes
Symmetries of activated complexes
复制标题
活化配合物的对称性
DOI：
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发表时间：
1968
期刊：
影响因子：
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通讯作者：
K. Laidler
中科院分区：
文献类型：
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作者：
J. Murrell;K. Laidler
以前的工作表明，在使用活化络合物理论计算速率时，应该忽略旋转配分函数中的对称数，并乘以一个统计因子;这个因子是反应物可以产生的活化络合物的等价形式的数量。如果选择的活化络合物具有如此高的对称度，以至于它可以形成一种以上的反应物或产物，则该过程可能导致错误。它是从多维势能面的考虑，一个单一的激活复合物不能存在于两个谷的交叉点;三个谷，例如，将产生三个独立的激活状态，其中每一个代表一对谷之间的最低通过。这一结论的影响被认为是参考几个反应，包括氢和碘之间。
Previous work has indicated that in calculating rates using activated-complex theory one should omit symmetry numbers from the rotational partition functions and multiply by a statistical factor; this factor is the number of equivalent forms of the activated complex that can arise from the reactants. This procedure can lead to error if the activated complex is chosen to have such a high degree of symmetry that it can form more than one form of the reactants or products. It is shown from a consideration of multi-dimensional potential-energy surfaces that a single activated complex cannot exist at the intersection of two valleys; three valleys, for example, will give rise to three separate activated states, each of which represents the lowest pass between a pair of valleys. The implications of this conclusion are considered with reference to several reactions, including that between hydrogen and iodine.