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

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 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.

Authors:
 [1];  [2];  [3]
+ Show Author Affiliations
  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:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1221826
Report Number(s):
LA-UR-15-23906
Journal ID: ISSN 0021-9606; TRN: US1500742
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mechanochemistry; energy landscape; transition states; conformation; vibrational spectra

Citation Formats

Subramanian, Gopinath, Mathew, Nithin, and Leiding, Jeffery A. A generalized force-modified potential energy surface (G-FMPES) for mechanochemical simulations. United States: N. p., 2015. Web. doi:10.1063/1.4932103.
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Subramanian, Gopinath, Mathew, Nithin, & Leiding, Jeffery A. A generalized force-modified potential energy surface (G-FMPES) for mechanochemical simulations. United States. https://doi.org/10.1063/1.4932103
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Subramanian, Gopinath, Mathew, Nithin, and Leiding, Jeffery A. Mon . "A generalized force-modified potential energy surface (G-FMPES) for mechanochemical simulations". United States. https://doi.org/10.1063/1.4932103. https://www.osti.gov/servlets/purl/1221826.
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@article{osti_1221826,
title = {A generalized force-modified potential energy surface (G-FMPES) for mechanochemical simulations},
author = {Subramanian, Gopinath and Mathew, Nithin and Leiding, Jeffery A.},
abstractNote = {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.},
doi = {10.1063/1.4932103},
journal = {Journal of Chemical Physics},
number = 13,
volume = 143,
place = {United States},
year = {Mon Oct 05 00:00:00 EDT 2015},
month = {Mon Oct 05 00:00:00 EDT 2015}
}
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