无交叉分界面外溶剂化反应的过渡态理论
Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces
摘要：
用过渡态理论计算速率常数的准确性关键取决于无重交叉分界面的正确确定。我们在这里表明，它是可能的，以确定这样的最佳分割面的系统与非马尔可夫摩擦。然而，一个更直接的方法来计算率的基础上不变的流形，并避免使用一个分割面，使用这种方法，我们得到了一个明确的表达式的速度跨越非谐势垒。我们的方法的优良性能的说明与应用程序的一个现实的模型LiNC $\rightleftharpoons$ LiCN异构化。
英文摘要：
The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing--free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non--Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface altogether, Using that method we obtain an explicit expression for the rate of crossing an anharmonic potential barrier. The excellent performance of our method is illustrated with an application to a realistic model for LiNC$\rightleftharpoons$LiCN isomerization.
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