A generalized force-modified potential energy surface for mechanochemical simulations.
A generalized force-modified potential energy surface for mechanochemical simulations.
复制标题
用于机械化学模拟的广义力修正势能面。
DOI：
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发表时间：
2015
影响因子：
4.4
通讯作者：
J. Leiding
中科院分区：
文献类型：
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作者：
G. Subramanian;N. Mathew;J. Leiding
我们通过计算感兴趣的静态量来描述空间变化的外部载荷对Born-Oppenheimer势能面（PES）产生的修改。用两种不同分子：乙烷和六氢-1,3,5-三硝基-s-三嗪（RDX）的电子结构计算（在HF/6-31G（∗∗）水平）举例说明了外部负载的影响。通过计算稳态点的过渡态和Hessian矩阵表明，空间变化的外载荷会使稳态点发生位移并改变PES的曲率，从而通过改变能量势垒和前因子来影响谐波跃迁速率。两种分子的谐波谱随着压缩“压力”的增加而发生蓝移。外荷载作用下，RDX-PES上的一些静止点消失，表明能量最小值与鞍点合并。
We describe the modifications that a spatially varying external load produces on a Born-Oppenheimer potential energy surface (PES) by calculating static quantities of interest. The effects of the external loads are exemplified using electronic structure calculations (at the HF/6-31G(∗∗) level) of two different molecules: ethane and hexahydro-1,3,5-trinitro-s-triazine (RDX). The calculated transition states and Hessian matrices of stationary points show that spatially varying external loads shift the stationary points and modify the curvature of the PES, thereby affecting the harmonic transition rates by altering both the energy barrier as well as the prefactor. The harmonic spectra of both molecules are blueshifted with increasing compressive "pressure." Some stationary points on the RDX-PES disappear under application of the external load, indicating the merging of an energy minimum with a saddle point.
影响因子：
15
作者：
Ong, Mitchell T.;Leiding, Jeff;Martinez, Todd J.
通讯作者：
Martinez, Todd J.