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

Abstract

Quasi-classical molecular dynamics simulations were used to study the energy relaxation of an initially non-rotating, vibrationally excited ( v = 4) hydroxyl radical (OH) in an Ar bath at 300 K and at high pressures from 50 atm to 400 atm. A Morse oscillator potential represented the OH, and two sets of interaction potentials were used based on whether the Ar-H potential was a Buckingham (Exp6) or a Lennard-Jones (LJ) potential. The vibrational and rotational energies were monitored for 25 000-90 000 ps for Exp6 trajectories and 5000 ps for LJ trajectories. Comparisons to measured vibrational relaxation rates show that Exp6 rates are superior. Simulated initial vibrational relaxation rates are linearly proportional to pressure, implying no effect of high-pressure breakdown in the isolated binary collision approximation. The vibrational decay curves upward from single-exponential decay. A model based on transition rates that exponentially depend on the anharmonic energy gap between vibrational levels fits the vibrational decay well at all pressures, suggesting that anharmonicity is a major cause of the curvature. Due to the competition of vibration-to-rotation energy transfer and bath gas relaxation, the rotational energy overshoots and then relaxes to its thermal value. Approximate models with adjustable rates for this competitionmore » successfully reproduced the rotational results. These models show that a large fraction of the vibrational energy loss is initially converted to rotational energy but that fraction decreases rapidly as the vibrational energy content of OH decreases. Finally, while simulated rates change dramatically between Exp6 and LJ potentials, the mechanisms remain the same.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1510323
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 11; 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; rotational relaxation; vibrational relaxation

Citation Formats

Chitsazi, Rezvan, and Wagner, Albert F. Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath. United States: N. p., 2019. Web. doi:10.1063/1.5063923.
Chitsazi, Rezvan, & Wagner, Albert F. Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath. United States. doi:10.1063/1.5063923.
Chitsazi, Rezvan, and Wagner, Albert F. Fri . "Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath". United States. doi:10.1063/1.5063923.
@article{osti_1510323,
title = {Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath},
author = {Chitsazi, Rezvan and Wagner, Albert F.},
abstractNote = {Quasi-classical molecular dynamics simulations were used to study the energy relaxation of an initially non-rotating, vibrationally excited (v = 4) hydroxyl radical (OH) in an Ar bath at 300 K and at high pressures from 50 atm to 400 atm. A Morse oscillator potential represented the OH, and two sets of interaction potentials were used based on whether the Ar-H potential was a Buckingham (Exp6) or a Lennard-Jones (LJ) potential. The vibrational and rotational energies were monitored for 25 000-90 000 ps for Exp6 trajectories and 5000 ps for LJ trajectories. Comparisons to measured vibrational relaxation rates show that Exp6 rates are superior. Simulated initial vibrational relaxation rates are linearly proportional to pressure, implying no effect of high-pressure breakdown in the isolated binary collision approximation. The vibrational decay curves upward from single-exponential decay. A model based on transition rates that exponentially depend on the anharmonic energy gap between vibrational levels fits the vibrational decay well at all pressures, suggesting that anharmonicity is a major cause of the curvature. Due to the competition of vibration-to-rotation energy transfer and bath gas relaxation, the rotational energy overshoots and then relaxes to its thermal value. Approximate models with adjustable rates for this competition successfully reproduced the rotational results. These models show that a large fraction of the vibrational energy loss is initially converted to rotational energy but that fraction decreases rapidly as the vibrational energy content of OH decreases. Finally, while simulated rates change dramatically between Exp6 and LJ potentials, the mechanisms remain the same.},
doi = {10.1063/1.5063923},
journal = {Journal of Chemical Physics},
number = 11,
volume = 150,
place = {United States},
year = {2019},
month = {3}
}

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