Collisional Deactivation of CO2(0001) and N2O(0001) by Toluene Isotopomers:  Near-Resonant Energy Transfer from N2O(0001)

Poel, Kathleen L.; Glavan, Corina M.; Alwahabi, Zeyad T.; King, Keith D.

doi:10.1021/jp9638806

Cited by 6 publications

(7 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…V − V Energy Transfer. Poel et al − have used the time-resolved IRF technique to study the vibrational deactivation of CO 2 (00 0 1) and N 2 O(00 0 1) by large polyatomic molecules (c-C 6 H 10 , c-C 6 H 12 , C 6 H 6 , C 6 D 6 , C 7 H 8 , C 7 D 8 , C 6 H 5 F, p -C 6 H 4 F 2 , C 6 HF 5 , and C 6 F 6 ) at ambient temperature (295 ± 2 K). Most previous measurements have been confined to deactivation of CO 2 (00 0 1) by small colliders (monatomics and small polyatomics).…”

Section: Energy Transfer Modelsmentioning

confidence: 99%

Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems

2001

Self Cite

View full text Add to dashboard Cite

The use of energy transfer data and models in describing nonequilibrium polyatomic reaction systems is discussed with particular emphasis on the information needed for modeling vibrational energy transfer. In the discussion, it is pointed out that key areas of energy transfer knowledge are still lacking and the available experimental data are limited in scope and are of uneven quality. Despite these limitations, it is still possible to carry out meaningful simulations of chemical systems in which vibrational energy transfer is important. The vibrational energy master equation, which is the basis for modeling, and various experiments and calculations that provide the basis for practical energy transfer models and parametrizations are described. Two examples of gas phase reaction systems are presented in which vibrational energy transfer is important. The decomposition of norbornene shows how energy transfer parameters can be obtained from measurements of shock-induced chemical reactions, but even the best such experiments provide only limited information about energy transfer. Chemically activated 2-methylhexyl radicals illustrate the complex reactions of multiple isomers connected by multiple isomerization pathways and reacting according to multiple decomposition pathways.

show abstract

Section: Energy Transfer Modelsmentioning

confidence: 99%

Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems

2001

Self Cite

View full text Add to dashboard Cite

show abstract

“…Gas-phase energy transfer in molecular collisions has been the subject of continuing interest in chemistry and physics for the past several decades. − In recent years, collisions involving large organic molecules have been studied extensively, revealing valuable information on the rates and the mechanisms of deactivation of the excited molecules through vibration−translation (VT) and/or vibration−vibration (VV) processes. Such collision processes as well as collision-induced intramolecular VV energy transfer are attractive systems for study, since a larger molecule can provide a number of near-resonant energy transfer pathways. − The importance of such a near-resonant condition has recently been examined by Poel, Alwahabi, and King in their study of energy transfer from N 2 O(00 0 1; 2224 cm -1 ) to large organic molecules. − Since the CD stretching frequencies of many deuterated hydrocarbons are 2224 ± 100 cm -1 , N 2 O(00 0 1) is a particularly useful reagent in preparing large organic molecules in an excited state.…”

Section: Introductionmentioning

confidence: 99%

“…Such collision processes as well as collision-induced intramolecular VV energy transfer are attractive systems for study, since a larger molecule can provide a number of near-resonant energy transfer pathways. [9][10][11][12][13][14][15][16][17][18] The importance of such a near-resonant condition has recently been examined by Poel, Alwahabi, and King in their study of energy transfer from N 2 O(00 0 1; 2224 cm -1 ) to large organic molecules. [9][10][11] Since the CD stretching frequencies of many deuterated hydrocarbons are 2224 ( 100 cm -1 , 19 N 2 O(00 0 1) is a particularly useful reagent in preparing large organic molecules in an excited state.…”

Section: Introductionmentioning

confidence: 99%

Principal Energy Transfer Pathways in the Collision of N₂O(00⁰1) with Toluene-d₈. A (WKB) Semiclassical Study

Shin

1999

J. Phys. Chem. A

View full text Add to dashboard Cite

Vibrational energy transfer from N2O(0001) to deuterated toluene has been studied by use of the Wentzel−Kramers−Brillouin (WKB) semiclassical procedure in the distorted-wave approximation in the temperature range of 100−500 K. Energy transfer to the CD stretch modes (νa‘ ‘ and νa‘) on the methyl group of C6D5CD3 is shown to be the principal pathway occurring through long-range interactions. The energy transfer to the CD stretch modes (ν7, ν20, and ν2) on the benzene ring are found to be of minor importance in removing vibrational energy from N2O(0001). Energy transfer to these ring modes is shown to occur through short-range interactions where the energy mismatch is supplied by the translational motion. In all cases, energy transfer probabilities decrease with increasing temperature.

show abstract

“…In recent years, collisions involving large organic molecules have been studied actively, revealing valuable information on the rates and the mechanisms of vibrational energy transfer. Large organic molecules can provide a number of near-resonant energy transfer pathways, − so they are important systems for studying the problem of vibration-to-vibration (VV) energy transfer. Except for the case of exact resonance, intermolecular VV energy transfer involves the energy mismatch Δ E , which has to be transferred to or from other motions such as translation (VT) or rotation (VR).…”

Section: Introductionmentioning

confidence: 99%

“…When the magnitude of Δ E is small, the translational motion of the colliding molecules can transfer it efficiently even at long range; i.e., the overall energy transfer process is VVT. Among such collision systems which have been studied are energy transfer between aromatic hydrocarbons and N 2 O(00°1) or CO 2 (00°1). − ,, Normal or deuterated hydrocarbons have their CH stretching frequencies in near resonance with the asymmetric stretch of these triatomic molecules and vibrations of many diatomic species such as DF, CO + , N 2 + and OH + . − Of these hydrocarbons, toluene has its CH stretching frequencies within 200 cm -1 of DF(1). In particular, toluene has two groups of CH stretches (the benzene ring and methyl CH modes) so the collision of this molecule with a vibrationally excited molecule such as DF(1) is a particularly attractive system for studying the competition among the two groups of modes for energy transfer and the mechanism for energy transfer, especially whether it is the short-range repulsive or long-range attractive part of the interaction energy which causes energy transfer.…”

Section: Introductionmentioning

confidence: 99%

Vibrational Energy Transfer from DF(1) to Toluene. Competition between the Benzene Ring CH and Methyl Group CH Stretches

Shin

2000

J. Phys. Chem. A

View full text Add to dashboard Cite

Vibrational energy transfer from DF(1) to toluene has been studied by use of the WKB semiclassical procedure in the distorted-wave approximation. Both methyl stretches (ν 4 , ν 17 , ν 28 ) and benzene ring CH stretches (ν 1 , ν 2 , ν 3 ) are within 200 cm -1 of the DF vibrational frequency. Transfer of this energy mismatch from translation to toluene accompanies the vibration-to-vibration energy exchange step (i.e., VVT). Energy transfer to these two groups of CH modes is treated in both long-range and short-range interactions. At 300 K, the most favored VVT channel is the energy transfer pathway from DF(1) to the ν 4 mode of the methyl CH stretch taking place at long interaction range. The ring CH modes suffer stronger perturbation by DF, but their excitation is not very efficient because they proceed with a larger energy mismatch. However, when the ring mode vibrational frequencies are changed to alter the energy mismatch toward the resonant case, energy transfer to the ring modes at long range becomes the principal energy transfer pathway. The short-range interaction model leads to smaller energy transfer probabilities which vary weakly with the energy mismatch. As temperature increases, probabilities calculated at long range decrease, whereas those calculated at short range increase.

show abstract

Collisional Deactivation of CO₂(00⁰1) and N₂O(00⁰1) by Toluene Isotopomers: Near-Resonant Energy Transfer from N₂O(00⁰1)

Cited by 6 publications

References 32 publications

Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems

Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems

Principal Energy Transfer Pathways in the Collision of N₂O(00⁰1) with Toluene-d₈. A (WKB) Semiclassical Study

Vibrational Energy Transfer from DF(1) to Toluene. Competition between the Benzene Ring CH and Methyl Group CH Stretches

Contact Info

Product

Resources

About

Collisional Deactivation of CO2(0001) and N2O(0001) by Toluene Isotopomers: Near-Resonant Energy Transfer from N2O(0001)

Cited by 6 publications

References 32 publications

Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems

Vibrational Energy Transfer Modeling of Nonequilibrium Polyatomic Reaction Systems

Principal Energy Transfer Pathways in the Collision of N2O(0001) with Toluene-d8. A (WKB) Semiclassical Study

Vibrational Energy Transfer from DF(1) to Toluene. Competition between the Benzene Ring CH and Methyl Group CH Stretches

Contact Info

Product

Resources

About

Collisional Deactivation of CO₂(00⁰1) and N₂O(00⁰1) by Toluene Isotopomers: Near-Resonant Energy Transfer from N₂O(00⁰1)

Principal Energy Transfer Pathways in the Collision of N₂O(00⁰1) with Toluene-d₈. A (WKB) Semiclassical Study