Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited CS2

György Lendvay, George C Schatz

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Collisional energy relaxation of highly excited CS2 in collisions with He and Xe is investigated by using classical trajectory methods to study the vibrational energy dependence of the average energy transfer per collision. This average energy transfer has been calculated by using two techniques: (1) direct simulation of the relaxation experiment by calculation of sequences of collisions suffered by an ensemble of hot molecules, and (2) evaluation of the energy transfer for specific internal energies by using microcanonical ensembles of excited molecules. Both methods provide energy-transfer values in good agreement with experiment and with each other. The negative of the average energy transfer per collision increases linearly with increasing CS2 energy if the collider is He and quadratically if the collider is Xe. These results are not especially sensitive to the inter-or intramolecular potentials, but the mass difference between He and Xe plays an important role. A detailed analysis of the trajectories indicates that the light collider participates in impulsive collisions, while the heavy collider participates in "slow" collisions in which the two colliders interact strongly for several vibrational periods. The validity of several different theories of the energy dependence of the energy transfer is investigated.

Original languageEnglish
Pages (from-to)8748-8753
Number of pages6
JournalJournal of Physical Chemistry
Volume95
Issue number22
Publication statusPublished - 1991

Fingerprint

Energy transfer
Colliding beam accelerators
energy transfer
collisions
energy
Trajectories
trajectories
Molecules
internal energy
molecules
Experiments
evaluation
simulation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited CS2. / Lendvay, György; Schatz, George C.

In: Journal of Physical Chemistry, Vol. 95, No. 22, 1991, p. 8748-8753.

Research output: Contribution to journalArticle

@article{905737c409c74d99a0c59e79f3e1be9d,
title = "Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited CS2",
abstract = "Collisional energy relaxation of highly excited CS2 in collisions with He and Xe is investigated by using classical trajectory methods to study the vibrational energy dependence of the average energy transfer per collision. This average energy transfer has been calculated by using two techniques: (1) direct simulation of the relaxation experiment by calculation of sequences of collisions suffered by an ensemble of hot molecules, and (2) evaluation of the energy transfer for specific internal energies by using microcanonical ensembles of excited molecules. Both methods provide energy-transfer values in good agreement with experiment and with each other. The negative of the average energy transfer per collision increases linearly with increasing CS2 energy if the collider is He and quadratically if the collider is Xe. These results are not especially sensitive to the inter-or intramolecular potentials, but the mass difference between He and Xe plays an important role. A detailed analysis of the trajectories indicates that the light collider participates in impulsive collisions, while the heavy collider participates in {"}slow{"} collisions in which the two colliders interact strongly for several vibrational periods. The validity of several different theories of the energy dependence of the energy transfer is investigated.",
author = "Gy{\"o}rgy Lendvay and Schatz, {George C}",
year = "1991",
language = "English",
volume = "95",
pages = "8748--8753",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - Energy dependence of energy transfer in the collisional relaxation of vibrationally highly excited CS2

AU - Lendvay, György

AU - Schatz, George C

PY - 1991

Y1 - 1991

N2 - Collisional energy relaxation of highly excited CS2 in collisions with He and Xe is investigated by using classical trajectory methods to study the vibrational energy dependence of the average energy transfer per collision. This average energy transfer has been calculated by using two techniques: (1) direct simulation of the relaxation experiment by calculation of sequences of collisions suffered by an ensemble of hot molecules, and (2) evaluation of the energy transfer for specific internal energies by using microcanonical ensembles of excited molecules. Both methods provide energy-transfer values in good agreement with experiment and with each other. The negative of the average energy transfer per collision increases linearly with increasing CS2 energy if the collider is He and quadratically if the collider is Xe. These results are not especially sensitive to the inter-or intramolecular potentials, but the mass difference between He and Xe plays an important role. A detailed analysis of the trajectories indicates that the light collider participates in impulsive collisions, while the heavy collider participates in "slow" collisions in which the two colliders interact strongly for several vibrational periods. The validity of several different theories of the energy dependence of the energy transfer is investigated.

AB - Collisional energy relaxation of highly excited CS2 in collisions with He and Xe is investigated by using classical trajectory methods to study the vibrational energy dependence of the average energy transfer per collision. This average energy transfer has been calculated by using two techniques: (1) direct simulation of the relaxation experiment by calculation of sequences of collisions suffered by an ensemble of hot molecules, and (2) evaluation of the energy transfer for specific internal energies by using microcanonical ensembles of excited molecules. Both methods provide energy-transfer values in good agreement with experiment and with each other. The negative of the average energy transfer per collision increases linearly with increasing CS2 energy if the collider is He and quadratically if the collider is Xe. These results are not especially sensitive to the inter-or intramolecular potentials, but the mass difference between He and Xe plays an important role. A detailed analysis of the trajectories indicates that the light collider participates in impulsive collisions, while the heavy collider participates in "slow" collisions in which the two colliders interact strongly for several vibrational periods. The validity of several different theories of the energy dependence of the energy transfer is investigated.

UR - http://www.scopus.com/inward/record.url?scp=0001413793&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001413793&partnerID=8YFLogxK

M3 - Article

VL - 95

SP - 8748

EP - 8753

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 22

ER -