Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5099050 · OSTI ID:1556908
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)
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; US Army Research Office (ARO); USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1556908
Alternate ID(s):
OSTI ID: 1542693
Journal Information:
Journal of Chemical Physics, Vol. 151, Issue 3; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (33)

Molecular-dynamics simulation of collisional energy transfer from vibrationally highly excited azulene in compressed CO2 journal June 1998
Molecular dynamics simulation of vibrational relaxation of highly excited molecules in fluids. II. Nonequilibrium simulation of azulene in CO2 and Xe journal March 1999
A unified model for simulating liquid and gas phase, intermolecular energy transfer: N 2 + C 6 F 6 collisions journal May 2014
Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath journal January 2015
Bath Model for N 2 + C 6 F 6 Gas-Phase Collisions. Details of the Intermolecular Energy Transfer Dynamics journal April 2015
Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N 2 Collisions journal February 2016
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
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
Non-statistical intermolecular energy transfer from vibrationally excited benzene in a mixed nitrogen-benzene bath journal October 2018
Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath journal March 2019
Chemical Dynamics Simulation of Energy Transfer: Propylbenzene Cation and N 2 Collisions journal February 2019
Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited carbon disulfide journal October 1991
Theoretical Studies of Solid Nitromethane journal September 2000
Molecular dynamics study of the melting of nitromethane journal November 2003
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
Quasiclassical trajectory calculations for the OH( X   2 Π) and OD( X   2 Π)+HBr reactions: Energy partitioning and rate constants journal December 1996
Gaussian Binning of the Vibrational Distributions for the Cl + CH 4 ( v 4/2 = 0, 1) → H + CH 3 Cl( n 1 n 2 n 3 n 4 n 5 n 6 ) Reactions journal July 2012
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
Shock-induced melting of (100)-oriented nitromethane: Energy partitioning and vibrational mode heating journal December 2009
Molecular Dynamics Simulations of Normal Mode Vibrational Energy Transfer in Liquid Nitromethane journal January 2004
Projection methods for obtaining intramolecular energy transfer rates from classical trajectory results: Application to 1,2‐difluoroethane journal November 1988
Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops journal July 1942
Gateway Modes in the Collisional Energy Transfer from Highly Vibrationally Excited CS 2 journal December 1997
Quasiclassical trajectory calculations of collisional energy transfer: the methyl internal rotor in ethane journal January 1999
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
Energy Transfer between Polyatomic Molecules. 1. Gateway Modes, Energy Transfer Quantities and Energy Transfer Probability Density Functions in Benzene−Benzene and Ar−Benzene Collisions † journal May 2005
The Kinetic Energy of Polyatomic Molecules journal September 1934

Figures / Tables (10)

Table I(p. 6)table Table I
Figure 1(p. 10)figure Figure 1
Figure 2(p. 12)figure Figure 2
Figure 3(p. 14)figure Figure 3
Figure 4(p. 15)figure Figure 4
Figure 5(p. 16)figure Figure 5
Figure 6(p. 17)figure Figure 6
Figure 7(p. 19)figure Figure 7
Figure 8(p. 20)figure Figure 8
Figure 9(p. 21)figure Figure 9

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Coriolis energy
normal mode analysis
rotational relaxation
vibrational relaxation