Multidimensional Marcus theory: An analysis of concerted reactions
Multidimensional Marcus theory: An analysis of concerted reactions
复制标题
DOI：
10.1021/ja961860b
复制
发表时间：
1996-12-25
影响因子：
15
通讯作者：
Guthrie, JP
中科院分区：
文献类型：
--
作者：
Guthrie, JP
通过与一维情况类比，已经导出了允许将马库斯理论应用于具有两个、三个或四个反应坐标维度的反应的方程。所有这些方程均基于反应坐标的四次近似； G(lambda) = ax(2) + bx(3) + cx(4)。最终方程仅需要每个维度的每个角中间势垒和内在势垒的能量作为输入。计算机程序已被编写为允许通过高维超空间的数值搜索来找到过渡态。这些程序允许检查涉及多个过程的潜在协同反应，数值探索表明，过渡态涉及多个反应坐标所必须满足的条件随着数量的增加而变得越来越严格，对于佯攻来说，基本上不可能同时改变四个坐标。
Equations permitting the application of Marcus theory to reactions with two, three, or four reaction coordinate dimensions have been derived by analogy with the one-dimensional case. All of these equations are based on the quartic approximation to the reaction coordinate; G(lambda) = ax(2) + bx(3) + cx(4). The final equations require as input only the energies of each corner intermediate and intrinsic barriers for each dimension. Computer programs have been written to allow finding of the transition state, by numerical search of the high dimensional hyperspace. These programs allow examination of potentially concerted reactions involving multiple processes, Numerical exploration shows that the conditions which must be met for a transition state to involve more than one reaction coordinate become increasingly stringent as the number increases, to the Feint that it is essentially impossible to have four coordinates changing at once.