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Quantum-chemistry-based force field for simulations of dimethylnitramine

Journal Article · · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
DOI:https://doi.org/10.1021/jp9834006· OSTI ID:335242
; ; ;  [1]
  1. Univ. of Utah, Salt Lake City, UT (United States)

The molecular geometries and conformational energies of nitramide and dimethylnitramine (DMNA), determined from high-level quantum chemistry calculations, have been used in parameterization of a classical potential function suitable for simulations of DMNA. A thorough investigation of basis set size and electron correlation effects on the geometry and conformational energies of nitramide, for which accurate experimental data exist, has allowed the authors to establish the level of theory required to obtain accurate geometries and energies for nitramine compounds. These investigations revealed the importance of electron correlation for both the geometries and relative conformational energies in nitramines. The quantum-chemistry-based force field for DMNA was validated by comparing gas- and liquid-phase properties obtained from molecular dynamics simulations with available experimental data. The gas-phase radial distribution function obtained from simulation is in good agreement with that obtained from electron diffraction experiments and is consistent with a C{sub s} ground-state geometry for DMNA as predicted by quantum chemistry. The pressure-volume-temperature properties and solubility parameters for the bulk liquid are in very good agreement with available experimental measurements. The correlation time and activation energy associated with molecular reorientation is found to be in good agreement with NMR measurements.

Sponsoring Organization:
Utah Univ., Salt Lake City, UT (United States); Lawrence Livermore National Lab., CA (United States)
OSTI ID:
335242
Journal Information:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 4 Vol. 103; ISSN 1089-5647; ISSN JPCBFK
Country of Publication:
United States
Language:
English

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