Unprejudiced identification of reaction mechanisms from biased transition path sampling.
Unprejudiced identification of reaction mechanisms from biased transition path sampling.
复制标题
从有偏差的转变路径采样中公正地识别反应机制。
作者：
D. Zahn
提出了一种从分子动力学模拟中无偏见地研究反应机理的方法。它结合了过渡路径抽样方法和偏置策略，该策略(A)允许优化跨越过渡状态表面的能量最小值的过渡路径。然后，该偏差被用来(B)寻找遵循不同机理路线的反应路径。在第一步中，对应于相同机构的相似轨迹的流形被简化为单一的特征动力学路径。然后，我们的方法允许系统地寻找进一步的反应机理和相关的能量势垒。它以二维势中的单个粒子为例，说明了在压力诱导下氦原子插入到C60巴克球分子中的相当复杂的过程。
A method for unprejudiced investigation of reaction mechanisms from molecular-dynamics simulations is presented. It combines the transition path sampling approach with a biasing strategy, which (a) allows optimization of transition paths crossing an energy minimum of the transition state surface. The bias is then used to (b) find reaction pathways, which follow different mechanistic routes. In the first step the manifold of similar trajectories that correspond to the same mechanism is reduced to a single characteristic dynamical path. Our method then allows a systematic search for further reaction mechanisms and the related energy barriers. It is illustrated at the example of a single particle in a two-dimensional potential and of the rather complex process of the pressure-induced insertion of a helium atom into a C60 buckyball molecule.