TY - JOUR
T1 - Non-statistical intermolecular energy transfer from vibrationally excited benzene in a mixed nitrogen-benzene bath
AU - Paul, Amit K.
AU - West, Niclas A.
AU - Winner, Joshua D.
AU - Bowersox, Rodney D.W.
AU - North, Simon W.
AU - Hase, William L.
N1 - Funding Information:
This material is based upon work supported by the Air Force Office of Scientific Research under AFOSR Award Nos. FA9550-12-1-0443, FA9550-16-0133, and FA9550-17-1-0107, and the Robert A. Welch Foundation under Grant No. D-0005. Support was also provided by the High Performance Computing Center (HPCC) at Texas Tech University, under the direction of Philip W. Smith. Parts of the computations were also performed on Robinson, a general computer cluster of the Department of Chemistry and Biochemistry, Texas Tech University, purchased by the NSF CRIF-MU Grant No. CHE-0840493. A.K.P. also thanks the computational facilities at the National Institute of Technology Meghalaya, India.
Publisher Copyright:
© 2018 Author(s).
PY - 2018/10/7
Y1 - 2018/10/7
N2 - A chemical dynamics simulation was performed to model experiments [N. A. West et al., J. Chem. Phys. 145, 014308 (2016)] in which benzene molecules are vibrationally excited to 148.1 kcal/mol within a N2-benzene bath. A significant fraction of the benzene molecules are excited, resulting in heating of the bath, which is accurately represented by the simulation. The interesting finding from the simulations is the non-statistical collisional energy transfer from the vibrationally excited benzene C6H6 ∗ molecules to the bath. The simulations find that at ∼10-7 s and 1 atm pressure there are four different final temperatures for C6H6 ∗ and the bath. N2 vibration is not excited and remains at the original bath temperature of 300 K. Rotation and translation degrees of freedom of both N2 and C6H6 in the bath are excited to a final temperature of ∼340 K. Energy transfer from the excited C6H6 ∗ molecules is more efficient to vibration of the C6H6 bath than its rotation and translation degrees of freedom, and the final vibrational temperature of the C6H6 bath is ∼453 K, if the average energy of each C6H6 vibration mode is assumed to be RT. There is no vibrational equilibration between C6H6 ∗ and the C6H6 bath molecules. When the simulations are terminated, the vibrational temperatures of the C6H6 ∗ and C6H6 bath molecules are ∼537 K and ∼453 K, respectively. An important question is the time scale for complete energy equilibration of the C6H6 ∗ and N2 and C6H6 bath system. At 1 atm and 300 K, the experimental V-T (vibration-translation) relaxation time for N2 is ∼10-4 s. The simulation time was too short for equilibrium to be attained, and the time for complete equilibration of C6H6 ∗ vibration with translation, rotation, and vibration of the bath was not determined.
AB - A chemical dynamics simulation was performed to model experiments [N. A. West et al., J. Chem. Phys. 145, 014308 (2016)] in which benzene molecules are vibrationally excited to 148.1 kcal/mol within a N2-benzene bath. A significant fraction of the benzene molecules are excited, resulting in heating of the bath, which is accurately represented by the simulation. The interesting finding from the simulations is the non-statistical collisional energy transfer from the vibrationally excited benzene C6H6 ∗ molecules to the bath. The simulations find that at ∼10-7 s and 1 atm pressure there are four different final temperatures for C6H6 ∗ and the bath. N2 vibration is not excited and remains at the original bath temperature of 300 K. Rotation and translation degrees of freedom of both N2 and C6H6 in the bath are excited to a final temperature of ∼340 K. Energy transfer from the excited C6H6 ∗ molecules is more efficient to vibration of the C6H6 bath than its rotation and translation degrees of freedom, and the final vibrational temperature of the C6H6 bath is ∼453 K, if the average energy of each C6H6 vibration mode is assumed to be RT. There is no vibrational equilibration between C6H6 ∗ and the C6H6 bath molecules. When the simulations are terminated, the vibrational temperatures of the C6H6 ∗ and C6H6 bath molecules are ∼537 K and ∼453 K, respectively. An important question is the time scale for complete energy equilibration of the C6H6 ∗ and N2 and C6H6 bath system. At 1 atm and 300 K, the experimental V-T (vibration-translation) relaxation time for N2 is ∼10-4 s. The simulation time was too short for equilibrium to be attained, and the time for complete equilibration of C6H6 ∗ vibration with translation, rotation, and vibration of the bath was not determined.
UR - http://www.scopus.com/inward/record.url?scp=85054394796&partnerID=8YFLogxK
U2 - 10.1063/1.5043139
DO - 10.1063/1.5043139
M3 - Article
C2 - 30292226
AN - SCOPUS:85054394796
VL - 149
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
SN - 0021-9606
IS - 13
M1 - 134101
ER -