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Finite temperature string method for the study of rare events

机译:有限温度串法研究稀有事件

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摘要

A method is presented for the study of rare events such as conformational changes arising in activated processes whose reaction coordinate is not known beforehand and for which the assumptions of transition state theory are invalid. The method samples the energy landscape adaptively and determines the isoprobability surfaces for the transition: by definition the trajectories initiated anywhere on one of these surfaces has equal probability to reach first one metastable set rather than the other. Upon weighting these surfaces by the equilibrium probability distribution, one obtains an effective transition pathway, i.e., a tube in configuration space inside which conformational changes occur with high probability, and the associated rate. The method is first validated on a simple two-dimensional example; then it is applied to a model of solid-solid transformation of a condensed system.
机译:提出了一种方法,用于研究稀有事件,例如在激活过程中产生的构象变化,该过程的反应坐标事先未知,并且对于过渡态理论的假设无效。该方法自适应地对能量分布进行采样,并确定过渡的等渗性表面:通过定义,在这些表面之一上任何地方发起的轨迹具有相等的概率到达第一个亚稳态集而不是另一个。通过平衡概率分布对这些表面进行加权后,便获得了一条有效的过渡路径,即配置空间中的一根管,在该管中以高概率发生构象变化及其相关速率。该方法首先在一个简单的二维示例中得到验证;然后将其应用于冷凝系统的固-固转化模型。

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