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Title: A generalized force-modified potential energy surface (G-FMPES) for mechanochemical simulations

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 The 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 blue-shifted 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.
 [1] ;  [2] ;  [3]
  1. Univ. of Southern Mississippi, Hattiesburg, MS (United States)
  2. Univ. of Missouri-Columbia, Columbia, MO (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0021-9606; TRN: US1500742
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 13; Journal ID: ISSN 0021-9606
American Institute of Physics (AIP)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
Country of Publication:
United States
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mechanochemistry; energy landscape; transition states; conformation; vibrational spectra