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Title: Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

Abstract

The vibrational and rotational mode-specific relaxations of CH3NO2 with 50 kcal/mol of initial internal energy in an argon bath is computed at 300 K at pressures of 10-400 atm. This work uses archived information from our previously published [J. Chem. Phys. 142, 014303 (2015)] molecular dynamics simulations and employs our previous published [J. Chem. Phys. 151, 034303 (2019)] method for projecting time-dependent Cartesian velocities onto normal mode eigenvectors. The computed relaxations cover three types of energies: vibrational, rotational, and Coriolis. In general, rotational and Coriolis relaxations in all modes are initially fast followed by an orders of magnitude slower relaxation. For all modes, that slower relaxation rate is approximately comparable to the vibrational relaxation rate. For all three types of energies, there are small-scale mode-to-mode variations. Of particular prominence is the exceptionally fast relaxation shared in common by the external rotation about the C-N axis, the internal hindered rotation of the CH3 group relative to the NO2 group, and the symmetric stretch of the CH3 group.

Authors:
 [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Ferris State Univ., Big Rapids, MI (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1756635
Alternate Identifier(s):
OSTI ID: 1651229
Grant/Contract Number:  
AC02-06CH11357; AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Chemical Kinetics
Additional Journal Information:
Journal Volume: 52; Journal Issue: 12; Journal ID: ISSN 0538-8066
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecular dynamics; pressure dependence; rotational relaxation; vibrational relaxation

Citation Formats

Rivera‐Rivera, Luis A., and Wagner, Albert F. Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath. United States: N. p., 2020. Web. doi:10.1002/kin.21415.
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Rivera‐Rivera, Luis A., & Wagner, Albert F. Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath. United States. https://doi.org/10.1002/kin.21415
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Rivera‐Rivera, Luis A., and Wagner, Albert F. Thu . "Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath". United States. https://doi.org/10.1002/kin.21415. https://www.osti.gov/servlets/purl/1756635.
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@article{osti_1756635,
title = {Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath},
author = {Rivera‐Rivera, Luis A. and Wagner, Albert F.},
abstractNote = {The vibrational and rotational mode-specific relaxations of CH3NO2 with 50 kcal/mol of initial internal energy in an argon bath is computed at 300 K at pressures of 10-400 atm. This work uses archived information from our previously published [J. Chem. Phys. 142, 014303 (2015)] molecular dynamics simulations and employs our previous published [J. Chem. Phys. 151, 034303 (2019)] method for projecting time-dependent Cartesian velocities onto normal mode eigenvectors. The computed relaxations cover three types of energies: vibrational, rotational, and Coriolis. In general, rotational and Coriolis relaxations in all modes are initially fast followed by an orders of magnitude slower relaxation. For all modes, that slower relaxation rate is approximately comparable to the vibrational relaxation rate. For all three types of energies, there are small-scale mode-to-mode variations. Of particular prominence is the exceptionally fast relaxation shared in common by the external rotation about the C-N axis, the internal hindered rotation of the CH3 group relative to the NO2 group, and the symmetric stretch of the CH3 group.},
doi = {10.1002/kin.21415},
journal = {International Journal of Chemical Kinetics},
number = 12,
volume = 52,
place = {United States},
year = {Thu Aug 20 00:00:00 EDT 2020},
month = {Thu Aug 20 00:00:00 EDT 2020}
}
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https://doi.org/10.1002/kin.21415
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