Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 132, Issue 9, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.3335817
Keywords
bonds (chemical); molecular configurations; molecular dynamics method; organic compounds; potential energy surfaces
Funding
- eDIKT initiative
- School of Chemistry, University of Edinburgh
- Royal Society
- U.S. Office of Naval Research [N000140510460]
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Path-integral molecular dynamics (PIMD) simulations with an empirical interaction potential have been used to determine the experimental equilibrium structure of solid nitromethane at 4.2 and 15 K. By comparing the time-averaged molecular structure determined in a PIMD simulation to the calculated minimum-energy (zero-temperature) molecular structure, we have derived structural corrections that describe the effects of thermal motion. These corrections were subsequently used to determine the equilibrium structure of nitromethane from the experimental time-averaged structure. We find that the corrections to the intramolecular and intermolecular bond distances, as well as to the torsion angles, are quite significant, particularly for those atoms participating in the anharmonic motion of the methyl group. Our results demonstrate that simple harmonic models of thermal motion may not be sufficiently accurate, even at low temperatures, while molecular simulations employing more realistic potential-energy surfaces can provide important insight into the role and magnitude of anharmonic atomic motions.
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