Vibrational Energy Transfer

Flynn, George W.; Parmenter, C. S.; Wodtke, Alec M.

doi:10.1021/jp953735c

Cited by 217 publications

(176 citation statements)

References 423 publications

Supporting

Mentioning

169

Contrasting

Order By: Relevance

“…This work confirmed the existence of what have been termed [20][21][22][23] multi-quantum (MQ) and sequential, single-quantum (SQ) mechanisms of energy transfer in this and related systems. The former process consists of direct population transfer between vibration states, often over many vibrational quanta, within a target molecule, CsH in this case.…”

Section: T V Of Csh(v;j) In H 2 500 Ksupporting

confidence: 78%

“…These findings mirror those reported by Wodtke et al on vibrationally excited O 2 and NO. [20][21][22][23] (iv) The experimental cross section for the initial, MQ fall of T v was calculated to be 4.6 ± 1.1 Å 2 .…”

Section: T V Of Csh(v;j) In H 2 500 Kmentioning

confidence: 99%

“…The MQ and SQ terminology for intra-molecular events in the processes of equilibration was introduced by Wodtke and co-workers [20][21][22][23] who demonstrated the existence of fast decay routes from excited O 2 , NO, and other diatomics, involving loss of many vibrational quanta from the initially excited state. Parmenter and co-workers also reported multiquantum vibration state exchange both in diatomic molecules and in excited polyatomics.…”

Section: T V Of Csh(v;j) In H 2 500 Kmentioning

confidence: 99%

See 2 more Smart Citations

Quantum state-resolved, bulk gas energetics: Comparison of theory and experiment

McCaffery

2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

Until very recently, the computational model of state-to-state energy transfer in large gas mixtures, introduced by the author and co-workers, has had little experimental data with which to assess the accuracy of its predictions. In a novel experiment, Alghazi et al. [Chem. Phys. 448, 76 (2015)] followed the equilibration of highly vibrationally excited CsH(D) in baths of H 2 (D 2 ) with simultaneous time-and quantum state-resolution. Modal temperatures of vibration, rotation, and translation for CsH(D) were obtained and presented as a function of pump-probe delay time. Here the data from this study are used as a test of the accuracy of the computational method, and in addition, the consequent changes in bath gas modal temperatures, not obtainable in the experiment, are predicted. Despite large discrepancies between initial CsH(D) vibrational states in the experiment and those available using the computational model, the quality of agreement is sufficient to conclude that the model's predictions constitute at least a very good representation of the overall equilibration that, for some measurements, is very accurate. Published by AIP Publishing. [http://dx

show abstract

Section: T V Of Csh(v;j) In H 2 500 Ksupporting

confidence: 78%

Section: T V Of Csh(v;j) In H 2 500 Kmentioning

confidence: 99%

Section: T V Of Csh(v;j) In H 2 500 Kmentioning

confidence: 99%

See 1 more Smart Citation

Quantum state-resolved, bulk gas energetics: Comparison of theory and experiment

McCaffery

2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Whereas early work focused principally on molecules in low vibrational levels, 27 the development of stimulated emission pumping 28 and of overtone pumping 29 has allowed investigation of species in highly excited vibrational states. 2 Light collision partners are much more effective quenchers of large vibrational energy gaps than heavy species for molecules in low and high vibrational states. Single quantum relaxation often dominates, even when the diatomic is highly excited and evidently there are limits to the amount of energy that may be released on collision however much is contained initially within vibrational modes.…”

Section: Relaxation Pathways In Polyatomic Moleculesmentioning

confidence: 99%

“…1 However the number of additional excitation and relaxation routes in polyatomic molecules brings new possibilities, raising fundamental questions concerning the dynamical behavior of molecules. [2][3][4][5][6] Parmenter, 2 Rice 3 among others have drawn attention to the extraordinarily selective nature of vibrational transfer ͑VT͒ in large molecules. Waclawik and Lawrance 4,5 demonstrated that angular momentum ͑AM͒ factors exercise a controlling influence on VT in excited benzene.…”

Section: Introductionmentioning

confidence: 99%

The role of angular momentum in collision-induced vibration–rotation relaxation in polyatomics

McCaffery

Osborne

Marsh

et al. 2004

The Journal of Chemical Physics

View full text Add to dashboard Cite

Vibrational relaxation of the 6 1 level of S 1 ( 1 B 2u ) benzene is analyzed using the angular momentum model of inelastic processes. Momentum-͑rotational͒ angular momentum diagrams illustrate energetic and angular momentum constraints on the disposal of released energy and the effect of collision partner on resultant benzene rotational excitation. A kinematic ''equivalent rotor'' model is introduced that allows quantitative prediction of rotational distributions from inelastic collisions in polyatomic molecules. The method was tested by predicting K-state distributions in glyoxal-Ne as well as J-state distributions in rotationally inelastic acetylene-He collisions before being used to predict J and K distributions from vibrational relaxation of 6 1 benzene by H 2 , D 2 , and CH 4 . Diagrammatic methods and calculations illustrate changes resulting from simultaneous collision partner excitation, a particularly effective mechanism in p-H 2 where some 70% of the available 6 1 →0 0 energy may be disposed into 0→2 rotation. These results support the explanation for branching ratios in 6 1 →0 0 relaxation given by Waclawik and Lawrance and the absence of this pathway for monatomic partners. Collision-induced vibrational relaxation in molecules represents competition between the magnitude of the energy gap of a potential transition and the ability of the colliding species to generate the angular momentum ͑rotational and orbital͒ needed for the transition to proceed. Transition probability falls rapidly as ⌬J increases and for a given molecule-collision partner pair will provide a limit to the gap that may be bridged. Energy constraints increase as collision partner mass increases, an effect that is amplified when J i Ͼ0. Large energy gaps are most effectively bridged using light collision partners. For efficient vibrational relaxation in polyatomics an additional requirement is that the molecular motion of the mode must be capable of generating molecular rotation on contact with the collision partner in order to meet the angular momentum requirements. We postulate that this may account for some of the striking propensities that characterize polyatomic energy transfer.

show abstract

Two-dimensional time-delayed coherent anti-Stokes Raman spectroscopy and wavepacket dynamics of high ground-state vibrations

Knopp

Pinkas

Prior

2000

J. Raman Spectrosc.

View full text Add to dashboard Cite

A novel approach to the preparation and monitoring of molecules in high vibrational levels in their electronic ground state is presented. An ultrashort laser pulse prepares a well defined wavepacket in the electronic excited state and, following the evolution of this wavepacket, the proper frequency and timing are selected to optimize its coupling back down to high vibrational levels in the ground state. The evolution of the wavepacket in the ground state is then monitored by a time‐delayed coherent scattering from the polarization that has been induced in the ground state by the first two pulses. The ability to populate vibrations as high as v = 26 for molecular iodine is demonstrated experimentally and the potential of the new method [which is termed (TD)2CARS] for further developments towards mode‐selective excitations is discussed. Copyright © 2000 John Wiley & Sons, Ltd.

show abstract

Vibrational Energy Transfer

Cited by 217 publications

References 423 publications

Quantum state-resolved, bulk gas energetics: Comparison of theory and experiment

Quantum state-resolved, bulk gas energetics: Comparison of theory and experiment

The role of angular momentum in collision-induced vibration–rotation relaxation in polyatomics

Two-dimensional time-delayed coherent anti-Stokes Raman spectroscopy and wavepacket dynamics of high ground-state vibrations

Contact Info

Product

Resources

About