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Title: Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath

Abstract

In our previous work [Rivera-Rivera et al., J. Chem. Phys. 142, 014303 (2015)], classical molecular dynamics simulations followed the relaxation, in a 300 K Ar bath at a pressure of 10-400 atm, of nitromethane (CH3NO2) instantaneously excited by statistically distributing 50 kcal/mol among all its internal degrees of freedom. Both rotational and vibrational energies decayed with nonexponential curves. In this present work, we explore mode-specific mechanisms at work in the decay process. With the separation of rotation and vibration developed by Rhee and Kim [J. Chem. Phys. 107, 1394 (1997)], one can show that the vibrational kinetic energy decomposes only into vibrational normal modes, while the rotational and Coriolis energies decompose into both vibrational and rotational normal modes. The saved CH3NO2 positions and momenta were converted into mode-specific energies whose decay was monitored over 1000 ps. Lastly, the results identify vibrational and rotational modes that promote/resist energy lost and drive nonexponential behavior.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Texas A & M Univ., College Station, TX (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Baker Univ., Baldwin City, KS (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; US Army Research Office (ARO)
OSTI Identifier:
1556908
Alternate Identifier(s):
OSTI ID: 1542693
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Coriolis energy; normal mode analysis; rotational relaxation; vibrational relaxation

Citation Formats

Rivera-Rivera, Luis A., Wagner, Albert F., and Perry, Jamin W. Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath. United States: N. p., 2019. Web. doi:10.1063/1.5099050.
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Rivera-Rivera, Luis A., Wagner, Albert F., & Perry, Jamin W. Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath. United States. https://doi.org/10.1063/1.5099050
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Rivera-Rivera, Luis A., Wagner, Albert F., and Perry, Jamin W. Tue . "Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath". United States. https://doi.org/10.1063/1.5099050. https://www.osti.gov/servlets/purl/1556908.
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@article{osti_1556908,
title = {Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath},
author = {Rivera-Rivera, Luis A. and Wagner, Albert F. and Perry, Jamin W.},
abstractNote = {In our previous work [Rivera-Rivera et al., J. Chem. Phys. 142, 014303 (2015)], classical molecular dynamics simulations followed the relaxation, in a 300 K Ar bath at a pressure of 10-400 atm, of nitromethane (CH3NO2) instantaneously excited by statistically distributing 50 kcal/mol among all its internal degrees of freedom. Both rotational and vibrational energies decayed with nonexponential curves. In this present work, we explore mode-specific mechanisms at work in the decay process. With the separation of rotation and vibration developed by Rhee and Kim [J. Chem. Phys. 107, 1394 (1997)], one can show that the vibrational kinetic energy decomposes only into vibrational normal modes, while the rotational and Coriolis energies decompose into both vibrational and rotational normal modes. The saved CH3NO2 positions and momenta were converted into mode-specific energies whose decay was monitored over 1000 ps. Lastly, the results identify vibrational and rotational modes that promote/resist energy lost and drive nonexponential behavior.},
doi = {10.1063/1.5099050},
journal = {Journal of Chemical Physics},
number = 3,
volume = 151,
place = {United States},
year = {Tue Jul 16 00:00:00 EDT 2019},
month = {Tue Jul 16 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.5099050
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Cited by: 6 works
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Figures / Tables:

Table I Table I: Nitromethane SRT Vibrational and Rotational Normal Modes.
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    Figures / Tables found in this record:

    Table I (p. 6)table
    Figure 1 (p. 10)figure
    Figure 2 (p. 12)figure
    Figure 3 (p. 14)figure
    Figure 4 (p. 15)figure
    Figure 5 (p. 16)figure
    Figure 6 (p. 17)figure
    Figure 7 (p. 19)figure
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    Figure 9 (p. 21)figure
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