TY - JOUR
T1 - Collisional Intermolecular Energy Transfer from a N2 Bath at Room Temperature to a Vibrationlly "cold" C6F6 Molecule Using Chemical Dynamics Simulations
AU - Paul, Amit K.
AU - Donzis, Diego
AU - Hase, William L.
N1 - Funding Information:
The research reported here is based upon work supported by the Air Force Office of Scientific Research (AFOSR) BRI grant FA 9550-12-1-0443 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 CHE-0840493.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/6/1
Y1 - 2017/6/1
N2 - Chemical dynamics simulations were performed to study collisional intermolecular energy transfer from a thermalized N2 bath at 300 K to vibrationally "cold" C6F6. The vibrational temperature of C6F6 is taken as 50 K, which corresponds to a classical vibrational energy of 2.98 kcal/mol. The temperature ratio between C6F6 and the bath is 1/6, the reciprocal of the same ratio for previous "hot" C6F6 simulations (J. Chem. Phys. 2014, 140, 194103). Simulations were also done for a C6F6 vibrational temperature of 0 K. The average energy of C6F6 versus time is well fit by a biexponential function which gives a slightly larger short time rate component, k1, but a four times smaller long time rate component, k2, compared to those obtained from the "hot" C6F6 simulations. The average energy transferred per collision depends on the difference between the average energy of C6F6 and the final C6F6 energy after equilibration with the bath, but not on the temperature ratio of C6F6 and the bath. The translational and rotational degrees of freedom of the N2 bath transfer their energies to the vibrational degrees of freedom of C6F6. The energies of the N2 vibrational mode and translational and rotational modes of C6F6 remain unchanged during the energy transfer. It is also found that the energy distribution of C6F6 broadens as energy is transferred from the bath, with an almost linear increase in the deviation of the C6F6 energies from the average C6F6 energy as the average energy of C6F6 increases.
AB - Chemical dynamics simulations were performed to study collisional intermolecular energy transfer from a thermalized N2 bath at 300 K to vibrationally "cold" C6F6. The vibrational temperature of C6F6 is taken as 50 K, which corresponds to a classical vibrational energy of 2.98 kcal/mol. The temperature ratio between C6F6 and the bath is 1/6, the reciprocal of the same ratio for previous "hot" C6F6 simulations (J. Chem. Phys. 2014, 140, 194103). Simulations were also done for a C6F6 vibrational temperature of 0 K. The average energy of C6F6 versus time is well fit by a biexponential function which gives a slightly larger short time rate component, k1, but a four times smaller long time rate component, k2, compared to those obtained from the "hot" C6F6 simulations. The average energy transferred per collision depends on the difference between the average energy of C6F6 and the final C6F6 energy after equilibration with the bath, but not on the temperature ratio of C6F6 and the bath. The translational and rotational degrees of freedom of the N2 bath transfer their energies to the vibrational degrees of freedom of C6F6. The energies of the N2 vibrational mode and translational and rotational modes of C6F6 remain unchanged during the energy transfer. It is also found that the energy distribution of C6F6 broadens as energy is transferred from the bath, with an almost linear increase in the deviation of the C6F6 energies from the average C6F6 energy as the average energy of C6F6 increases.
UR - http://www.scopus.com/inward/record.url?scp=85020441301&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.7b00948
DO - 10.1021/acs.jpca.7b00948
M3 - Article
C2 - 28485962
AN - SCOPUS:85020441301
VL - 121
SP - 4049
EP - 4057
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 21
ER -