Pressure Effects on the Relaxation of an Excited Ethane Molecule in High-Pressure Bath Gases

Hren, Zackary R.; Lazarock, Chad R.; Vincent, Tasha A.; Rivera-Rivera, Luis A.; Wagner, Albert F.

doi:10.1021/acs.jpca.1c05838

Title: Pressure Effects on the Relaxation of an Excited Ethane Molecule in High-Pressure Bath Gases

Journal Article · Tue Sep 28 00:00:00 EDT 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.1c05838· OSTI ID:1878222

Hren, Zackary R. ^[1]; Lazarock, Chad R. ^[1]; Vincent, Tasha A. ^[1]; Rivera-Rivera, Luis A. ^[1];

^[2]

Ferris State University, Big Rapids, MI (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Here, we use molecular dynamics to calculate the rotational and vibrational energy relaxation of C₂H₆ in Ar, Kr, and Xe bath gases over a pressure range of 10 to 400 atm and at temperatures of 300 K and 800 K. The C₂H₆ is instantaneously excited by 80 kcal/mol randomly distributed into both vibrational and rotational modes. The computed relaxation rates show little sensitivity to the identity of the noble gas in the bath. Vibrational relaxation rates show a non-linear pressure dependence at 300 K. At 800 K the reduced range of bath gas densities covered by the range of pressures do not yet show any non-linearity in the pressure dependence. Rotational relaxation is characterized with two relaxation rates. The slower rate is comparable to the vibrational relaxation rate. The faster rate has a linear pressure dependence at 300 K but an irregular, nonlinear pressure dependence at 800 K. To understand this, a model was developed based on approximating the periodic box used in the molecular dynamics simulations by an equal-volume collection of cubes where each cube is sized to allow only single occupancy by the noble gas or the molecule. Combinatorial statistics then leads to a pressure and temperature dependent analytic distribution of the bath gas species the molecule encounters in a collision. This distribution, the dissociation energy of molecule/bath gas complexes and bath gas clusters, and the computed energy release per collision combine to show that only at 300 K is the energy release sufficient to dissociate likely complexes and clusters. This suggests that persistent and pressure-dependent clusters and complexes at 800 K may be responsible for the non-linear pressure dependence of rotational relaxation.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; American Chemical Society (ACS) Petroleum Research Fund; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; ACS PRF# 60523-UNI6; ACI-1548562

OSTI ID:: 1878222

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 125, Issue 39; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Computer-Intensive Methods in Statistics Diaconis, Persi; Efron, Bradley Scientific American, Vol. 248, Issue 5 https://doi.org/10.1038/scientificamerican0583-116	journal	May 1983
Interaction of the van der Waals Type Between Three Atoms Axilrod, B. M.; Teller, E. The Journal of Chemical Physics, Vol. 11, Issue 6 https://doi.org/10.1063/1.1723844	journal	June 1943
Non-statistical intermolecular energy transfer from vibrationally excited benzene in a mixed nitrogen-benzene bath Paul, Amit K.; West, Niclas A.; Winner, Joshua D. The Journal of Chemical Physics, Vol. 149, Issue 13 https://doi.org/10.1063/1.5043139	journal	October 2018
High pressure, high temperature shock tube studies of ethane pyrolysis and oxidation Tranter, Robert S.; Sivaramakrishnan, Raghu; Brezinsky, Kenneth Physical Chemistry Chemical Physics, Vol. 4, Issue 11 https://doi.org/10.1039/b110702j	journal	March 2002
Two-stage ignition in HCCI combustion and HCCI control by fuels and additives Tanaka, S. Combustion and Flame, Vol. 132, Issue 1-2 https://doi.org/10.1016/S0010-2180(02)00457-1	journal	January 2003
The spectrum and ground state potential curve of Ar ₂ Colbourn, E. A.; Douglas, A. E. The Journal of Chemical Physics, Vol. 65, Issue 5 https://doi.org/10.1063/1.433319	journal	September 1976
Reconsidering Dispersion Potentials: Reduced Cutoffs in Mesh-Based Ewald Solvers Can Be Faster Than Truncation Isele-Holder, Rolf E.; Mitchell, Wayne; Hammond, Jeff R. Journal of Chemical Theory and Computation, Vol. 9, Issue 12 https://doi.org/10.1021/ct4004614	journal	November 2013
Normal mode analysis on the relaxation of an excited nitromethane molecule in argon bath Rivera-Rivera, Luis A.; Wagner, Albert F.; Perry, Jamin W. The Journal of Chemical Physics, Vol. 151, Issue 3 https://doi.org/10.1063/1.5099050	journal	July 2019
Pressure and Temperature Dependence of the Recombination of p -Fluorobenzyl Radicals Lee, Changyoul; Luther, Klaus; Oum, Kawon The Journal of Physical Chemistry A, Vol. 110, Issue 8 https://doi.org/10.1021/jp056944y	journal	February 2006
High-pressure oxidation of ethane Hashemi, Hamid; Jacobsen, Jon G.; Rasmussen, Christian T. Combustion and Flame, Vol. 182 https://doi.org/10.1016/j.combustflame.2017.03.028	journal	August 2017
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Vibrational Energy Transfer Flynn, George W.; Parmenter, Charles S.; Wodtke, Alec M. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp953735c	journal	January 1996
Gateway Modes in the Collisional Energy Transfer from Highly Vibrationally Excited CS ₂ Lendvay, György The Journal of Physical Chemistry A, Vol. 101, Issue 49 https://doi.org/10.1021/jp972150a	journal	December 1997
Experimental and kinetic study of autoignition in methane/ethane/air and methane/propane/air mixtures under engine-relevant conditions Huang, J.; Bushe, W. K. Combustion and Flame, Vol. 144, Issue 1-2 https://doi.org/10.1016/j.combustflame.2005.06.013	journal	January 2006
Chemical Dynamics Simulation of Energy Transfer: Propylbenzene Cation and N ₂ Collisions Kim, Hyunsik; Bhandari, Hum Nath; Pratihar, Subha The Journal of Physical Chemistry A, Vol. 123, Issue 12 https://doi.org/10.1021/acs.jpca.9b00111	journal	February 2019
Pressure effects on the relaxation of an excited hydrogen peroxyl radical in an Argon bath Perry, Jamin W.; Wagner, Albert F. Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.06.054	journal	January 2017
Crossed beams and theoretical studies of the dynamics of hyperthermal collisions between Ar and ethane Brunsvold, Amy L.; Garton, Donna J.; Minton, Timothy K. The Journal of Chemical Physics, Vol. 121, Issue 23 https://doi.org/10.1063/1.1815271	journal	December 2004
An Introduction to the Bootstrap Efron, Bradley; Tibshirani, Robert J. Chapman and Hall/CRC https://doi.org/10.1007/978-1-4899-4541-9	book	January 1993
State-of-the-art ab initio potential energy curve for the xenon atom pair and related spectroscopic and thermophysical properties Hellmann, Robert; Jäger, Benjamin; Bich, Eckard The Journal of Chemical Physics, Vol. 147, Issue 3 https://doi.org/10.1063/1.4994267	journal	July 2017
Theoretical Unimolecular Kinetics for CH ₄ + M ⇄ CH ₃ + H + M in Eight Baths, M = He, Ne, Ar, Kr, H ₂ , N ₂ , CO, and CH ₄ Jasper, Ahren W.; Miller, James A. The Journal of Physical Chemistry A, Vol. 115, Issue 24 https://doi.org/10.1021/jp200048n	journal	June 2011
Efficient microcanonical sampling for a preselected total angular momentum Nyman, Gunnar; Nordholm, Sture; Schranz, Harold W. The Journal of Chemical Physics, Vol. 93, Issue 9 https://doi.org/10.1063/1.458945	journal	November 1990
ChemNetworks: A complex network analysis tool for chemical systems Ozkanlar, Abdullah; Clark, Aurora E. Journal of Computational Chemistry, Vol. 35, Issue 6 https://doi.org/10.1002/jcc.23506	journal	December 2013
Bond Dissociation Energies of Organic Molecules Blanksby, Stephen J.; Ellison, G. Barney Accounts of Chemical Research, Vol. 36, Issue 4 https://doi.org/10.1021/ar020230d	journal	April 2003
Collisional Energy Transfer from Highly Vibrationally Excited Radicals Is Very Efficient Wilhelm, Michael J.; Nikow, Matthew; Smith, Jonathan M. The Journal of Physical Chemistry Letters, Vol. 4, Issue 1 https://doi.org/10.1021/jz301761e	journal	December 2012
Mode‐specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath Rivera‐Rivera, Luis A.; Wagner, Albert F. International Journal of Chemical Kinetics, Vol. 52, Issue 12 https://doi.org/10.1002/kin.21415	journal	August 2020
Energy transfer in master equation simulations: A new approach Barker, John R. International Journal of Chemical Kinetics, Vol. 41, Issue 12 https://doi.org/10.1002/kin.20447	journal	December 2009
Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems Barker, John R.; Yoder, Laurie M.; King, Keith D. The Journal of Physical Chemistry A, Vol. 105, Issue 5 https://doi.org/10.1021/jp002077f	journal	February 2001
A unified model for simulating liquid and gas phase, intermolecular energy transfer: N ₂ + C ₆ F ₆ collisions Paul, Amit K.; Kohale, Swapnil C.; Pratihar, Subha The Journal of Chemical Physics, Vol. 140, Issue 19 https://doi.org/10.1063/1.4875516	journal	May 2014
Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath Rivera-Rivera, Luis A.; Wagner, Albert F.; Sewell, Thomas D. The Journal of Chemical Physics, Vol. 142, Issue 1 https://doi.org/10.1063/1.4904314	journal	January 2015
The classical equation of state of gaseous helium, neon and argon Buckingham, R. A. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 168, Issue 933, p. 264-283 https://doi.org/10.1098/rspa.1938.0173	journal	October 1938
A Competition between Dissociation Pathway and Energy Transfer Pathway: Unimolecular Dissociation of a Benzene–Hexafluorobenzene Complex in Nitrogen Bath Ahamed, Sk. Samir; Mahanta, Himashree; Paul, Amit K. The Journal of Physical Chemistry A, Vol. 123, Issue 50 https://doi.org/10.1021/acs.jpca.9b07258	journal	November 2019
Ethane oxidation at elevated pressures in the intermediate temperature regime: Experiments and modeling Hunter, T. Combustion and Flame, Vol. 104, Issue 4 https://doi.org/10.1016/0010-2180(95)00154-9	journal	March 1996
Intermolecular vibrational energy transfer in thermal unimolecular systems Tardy, D. C.; Rabinovitch, B. S. Chemical Reviews, Vol. 77, Issue 3 https://doi.org/10.1021/cr60307a004	journal	June 1977
Ignition Characteristics of Ethane and Its Roles in Natural Gas for HCCI Engine Operation Tanaka, Hiroki; Kobayashi, Kazunobu; Sako, Takahiro SAE International Journal of Fuels and Lubricants, Vol. 8, Issue 2 https://doi.org/10.4271/2015-01-0811	journal	April 2015
Bath Model for N ₂ + C ₆ F ₆ Gas-Phase Collisions. Details of the Intermolecular Energy Transfer Dynamics Paul, Amit K.; Kohale, Swapnil C.; Hase, William L. The Journal of Physical Chemistry C, Vol. 119, Issue 26 https://doi.org/10.1021/jp512931n	journal	April 2015
Chemical Dynamics Simulations of Energy Transfer for Propylbenzene Cation and He Collisions Kim, Hyunsik; Saha, Biswajit; Pratihar, Subha The Journal of Physical Chemistry A, Vol. 121, Issue 40 https://doi.org/10.1021/acs.jpca.7b07982	journal	October 2017
Modeling high pressure ethane oxidation and pyrolysis Naik, Chitralkumar V.; Dean, Anthony M. Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.05.057	journal	January 2009
Ab initio calculations of the Ar-ethane intermolecular potential energy surface using bond function basis sets Zhang, Jian-Dong; Li, Shu-Jin; Tao, Fu-Ming Journal of Computational Chemistry, Vol. 34, Issue 8 https://doi.org/10.1002/jcc.23179	journal	November 2012
Pressure effects on the vibrational and rotational relaxation of vibrationally excited OH (ν, J ) in an argon bath Chitsazi, Rezvan; Wagner, Albert F. The Journal of Chemical Physics, Vol. 150, Issue 11 https://doi.org/10.1063/1.5063923	journal	March 2019
Development and application of a particle-particle particle-mesh Ewald method for dispersion interactions Isele-Holder, Rolf E.; Mitchell, Wayne; Ismail, Ahmed E. The Journal of Chemical Physics, Vol. 137, Issue 17 https://doi.org/10.1063/1.4764089	journal	November 2012
Energy transfer in highly excited large polyatomic molecules Oref, I.; Tardy, D. C. Chemical Reviews, Vol. 90, Issue 8 https://doi.org/10.1021/cr00106a003	journal	December 1990
Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N ₂ Collisions Kim, Hyunsik; Paul, Amit K.; Pratihar, Subha The Journal of Physical Chemistry A, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpca.6b00893	journal	February 2016
Investigation of ethane pyrolysis and oxidation at high pressures using global optimization based on shock tube data Samu, Viktor; Varga, Tamás; Brezinsky, Kenneth Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.05.039	journal	January 2017
Collisional Energy Transfer Probability Densities P ( E , J ; E′ , J′ ) for Monatomics Colliding with Large Molecules Barker, John R.; Weston, Ralph E. The Journal of Physical Chemistry A, Vol. 114, Issue 39 https://doi.org/10.1021/jp106443d	journal	October 2010
State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas Jäger, Benjamin; Hellmann, Robert; Bich, Eckard The Journal of Chemical Physics, Vol. 144, Issue 11 https://doi.org/10.1063/1.4943959	journal	March 2016
High-pressure single-pulse shock tube investigation of rich and stoichiometric ethane oxidation Tranter, R. S.; Amoorthy, H. Ram; Raman, A. Proceedings of the Combustion Institute, Vol. 29, Issue 1 https://doi.org/10.1016/S1540-7489(02)80156-0	journal	January 2002
Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited carbon disulfide Lendvay, Gyorgy; Schatz, George C. The Journal of Physical Chemistry, Vol. 95, Issue 22 https://doi.org/10.1021/j100175a061	journal	October 1991
Kinetics and mechanism of partial oxidation of ethane to ethylene and acetic acid over MoV type catalysts Rahman, Faizur; Loughlin, Kevin F.; Al-Saleh, Muhammad A. Applied Catalysis A: General, Vol. 375, Issue 1 https://doi.org/10.1016/j.apcata.2009.11.026	journal	February 2010
Computers and the Theory of Statistics: Thinking the Unthinkable Efron, Bradley SIAM Review, Vol. 21, Issue 4 https://doi.org/10.1137/1021092	journal	October 1979
Experimental study of a low pressure stoichiometric premixed methane, methane/ethane, methane/ethane/propane and synthetic natural gas flames Turbiez, A.; El Bakali, A.; Pauwels, J. F. Fuel, Vol. 83, Issue 7-8 https://doi.org/10.1016/j.fuel.2003.10.017	journal	May 2004
An efficient microcanonical sampling procedure for molecular systems Schranz, Harold W.; Nordholm, Sture; Nyman, Gunnar The Journal of Chemical Physics, Vol. 94, Issue 2 https://doi.org/10.1063/1.460008	journal	January 1991
Collisional Energy Transfer in Highly Excited Molecules Houston, Paul L.; Conte, Riccardo; Bowman, Joel M. The Journal of Physical Chemistry A, Vol. 118, Issue 36 https://doi.org/10.1021/jp506202g	journal	August 2014
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Pairwise-additive analytic potential for the Ar–CH3CH3 van der Waals complex Cooper, J. R.; Moazzen-Ahmadi, N. Chemical Physics Letters, Vol. 444, Issue 1-3 https://doi.org/10.1016/j.cplett.2007.06.129	journal	August 2007
Efficient microcanonical sampling for triatomic molecular systems: Exact distributions verified Nyman, Gunnar; Rynefors, Kjell; Holmlid, Leif The Journal of Chemical Physics, Vol. 88, Issue 6 https://doi.org/10.1063/1.453906	journal	March 1988
Ethane oxidation and pyrolysis from 5 bar to 1000 bar: Experiments and simulation: Ethane Oxidation and Pyrolysis from 5 Bar to 1000 Bar: Experiments and Simulation Tranter, R. S.; Raman, A.; Sivaramakrishnan, R. International Journal of Chemical Kinetics, Vol. 37, Issue 5 https://doi.org/10.1002/kin.20067	journal	March 2005
Comparative Kinetic Analysis of Ethane Pyrolysis at 0.1 and 2.0 MPa Saldana, Mario H.; Bogin, Gregory E.; Wang, Kun Energy & Fuels, Vol. 30, Issue 11 https://doi.org/10.1021/acs.energyfuels.6b01752	journal	October 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 Paul, Amit K.; Donzis, Diego; Hase, William L. The Journal of Physical Chemistry A, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpca.7b00948	journal	May 2017
Theoretical Study of the Ar−, Kr−, and Xe−CH ₄ , −CF ₄ Intermolecular Potential-Energy Surfaces Alexander, William A.; Troya, Diego The Journal of Physical Chemistry A, Vol. 110, Issue 37 https://doi.org/10.1021/jp063398f	journal	August 2006
Theoretical Study of the Dynamics of Ar Collisions with C ₂ H ₆ and C ₂ F ₆ at Hyperthermal Energy Tasić, Uroš; Hein, Pyae; Troya, Diego The Journal of Physical Chemistry A, Vol. 111, Issue 18 https://doi.org/10.1021/jp071287q	journal	April 2007

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