Document Type
Article
Publication Date
10-7-2015
School
Polymer Science and Engineering
Abstract
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.
Publication Title
Journal of Chemical Physics
Volume
143
Issue
13
Recommended Citation
Subramanian, G.,
Mathew, N.,
Leiding, J.
(2015). A Generalized Force-Modified Potential Energy Surface For Mechanochemical Simulations. Journal of Chemical Physics, 143(13).
Available at: https://aquila.usm.edu/fac_pubs/18664
Comments
© The Journal of Chemical Physics.
Published Version at 10.1063/1.4932103