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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 (CH 3NO 2) 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 CH 3NO 2 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]
  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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; US Army Research Office (ARO); USDOE
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.
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. doi:10.1063/1.5099050.
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. doi:10.1063/1.5099050.
@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 = {2019},
month = {7}
}

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Works referenced in this record:

Molecular-dynamics simulation of collisional energy transfer from vibrationally highly excited azulene in compressed CO2
journal, June 1998

  • Heidelbach, C.; Fedchenia, I. I.; Schwarzer, D.
  • The Journal of Chemical Physics, Vol. 108, Issue 24
  • DOI: 10.1063/1.476474

Molecular dynamics simulation of vibrational relaxation of highly excited molecules in fluids. II. Nonequilibrium simulation of azulene in CO2 and Xe
journal, March 1999

  • Heidelbach, C.; Vikhrenko, V. S.; Schwarzer, D.
  • The Journal of Chemical Physics, Vol. 110, Issue 11
  • DOI: 10.1063/1.478423

A unified model for simulating liquid and gas phase, intermolecular energy transfer: N 2 + C 6 F 6 collisions
journal, May 2014

  • Paul, Amit K.; Kohale, Swapnil C.; Pratihar, Subha
  • The Journal of Chemical Physics, Vol. 140, Issue 19
  • DOI: 10.1063/1.4875516

Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath
journal, January 2015

  • Rivera-Rivera, Luis A.; Wagner, Albert F.; Sewell, Thomas D.
  • The Journal of Chemical Physics, Vol. 142, Issue 1
  • DOI: 10.1063/1.4904314

Bath Model for N 2 + C 6 F 6 Gas-Phase Collisions. Details of the Intermolecular Energy Transfer Dynamics
journal, April 2015

  • Paul, Amit K.; Kohale, Swapnil C.; Hase, William L.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/jp512931n

Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N 2 Collisions
journal, February 2016

  • Kim, Hyunsik; Paul, Amit K.; Pratihar, Subha
  • The Journal of Physical Chemistry A, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpca.6b00893

Collisional Intermolecular Energy Transfer from a N 2 Bath at Room Temperature to a Vibrationlly “Cold” C 6 F 6 Molecule Using Chemical Dynamics Simulations
journal, May 2017

  • Paul, Amit K.; Donzis, Diego; Hase, William L.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 21
  • DOI: 10.1021/acs.jpca.7b00948

Pressure effects on the relaxation of an excited hydrogen peroxyl radical in an Argon bath
journal, January 2017


Chemical Dynamics Simulations of Energy Transfer for Propylbenzene Cation and He Collisions
journal, October 2017

  • Kim, Hyunsik; Saha, Biswajit; Pratihar, Subha
  • The Journal of Physical Chemistry A, Vol. 121, Issue 40
  • DOI: 10.1021/acs.jpca.7b07982

Non-statistical intermolecular energy transfer from vibrationally excited benzene in a mixed nitrogen-benzene bath
journal, October 2018

  • Paul, Amit K.; West, Niclas A.; Winner, Joshua D.
  • The Journal of Chemical Physics, Vol. 149, Issue 13
  • DOI: 10.1063/1.5043139

Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath
journal, March 2019

  • Chitsazi, Rezvan; Wagner, Albert F.
  • The Journal of Chemical Physics, Vol. 150, Issue 11
  • DOI: 10.1063/1.5063923

Chemical Dynamics Simulation of Energy Transfer: Propylbenzene Cation and N 2 Collisions
journal, February 2019

  • Kim, Hyunsik; Bhandari, Hum Nath; Pratihar, Subha
  • The Journal of Physical Chemistry A, Vol. 123, Issue 12
  • DOI: 10.1021/acs.jpca.9b00111

Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited carbon disulfide
journal, October 1991

  • Lendvay, Gyorgy; Schatz, George C.
  • The Journal of Physical Chemistry, Vol. 95, Issue 22
  • DOI: 10.1021/j100175a061

Theoretical Studies of Solid Nitromethane
journal, September 2000

  • Sorescu, Dan C.; Rice, Betsy M.; Thompson, Donald L.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 35
  • DOI: 10.1021/jp000942q

Molecular dynamics study of the melting of nitromethane
journal, November 2003

  • Agrawal, Paras M.; Rice, Betsy M.; Thompson, Donald L.
  • The Journal of Chemical Physics, Vol. 119, Issue 18
  • DOI: 10.1063/1.1612915

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Some Studies Concerning Rotating Axes and Polyatomic Molecules
journal, April 1935


The Kinetic Energy of Polyatomic Molecules
journal, June 1939

  • Sayvetz, Aaron
  • The Journal of Chemical Physics, Vol. 7, Issue 6
  • DOI: 10.1063/1.1750455

Quasiclassical trajectory calculations for the OH( X2 Π) and OD( X2 Π)+HBr reactions: Energy partitioning and rate constants
journal, December 1996

  • Nizamov, B.; Setser, D. W.; Wang, H.
  • The Journal of Chemical Physics, Vol. 105, Issue 22
  • DOI: 10.1063/1.472855

Dynamics and Novel Mechanisms of S N 2 Reactions on ab Initio Analytical Potential Energy Surfaces
journal, October 2017


Mode-specific energy analysis for rotating-vibrating triatomic molecules in classical trajectory simulation
journal, August 1997

  • Rhee, Young Min; Kim, Myung Soo
  • The Journal of Chemical Physics, Vol. 107, Issue 5
  • DOI: 10.1063/1.474493

Shock-induced melting of (100)-oriented nitromethane: Energy partitioning and vibrational mode heating
journal, December 2009

  • Dawes, Richard; Siavosh-Haghighi, Ali; Sewell, Thomas D.
  • The Journal of Chemical Physics, Vol. 131, Issue 22
  • DOI: 10.1063/1.3271349

Molecular Dynamics Simulations of Normal Mode Vibrational Energy Transfer in Liquid Nitromethane
journal, January 2004

  • Kabadi, Vinayak N.; Rice, Betsy M.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 4
  • DOI: 10.1021/jp035975v

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops
journal, July 1942

  • Pitzer, Kenneth S.; Gwinn, William D.
  • The Journal of Chemical Physics, Vol. 10, Issue 7
  • DOI: 10.1063/1.1723744

Gateway Modes in the Collisional Energy Transfer from Highly Vibrationally Excited CS 2
journal, December 1997

  • Lendvay, György
  • The Journal of Physical Chemistry A, Vol. 101, Issue 49
  • DOI: 10.1021/jp972150a

Quasiclassical trajectory calculations of collisional energy transfer: the methyl internal rotor in ethane
journal, January 1999

  • Linhananta, Apichart; Lim, Kieran F.
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 15
  • DOI: 10.1039/a902118c

The steric hindrance of methyl groups in collisional quenching of highly vibrationally excited methyl-substituted pyrazines by He, Ar, and Kr
journal, March 2001


Vibrational energy redistribution in polyatomic liquids: 3D infrared–Raman spectroscopy
journal, May 2001


CH2I2 fundamental vibrational relaxation in solution studied by transient electronic absorption spectroscopy
journal, October 2001

  • Cheatum, Christopher M.; Heckscher, Max M.; Bingemann, Dieter
  • The Journal of Chemical Physics, Vol. 115, Issue 15
  • DOI: 10.1063/1.1404393