Vibrational energy flow within excited electronic states of large molecules

Parmenter, C. S.

doi:10.1021/j100207a001

Cited by 190 publications

(72 citation statements)

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“…Parmenter and co-workers also reported multiquantum vibration state exchange both in diatomic molecules and in excited polyatomics. 28,29 The existence of MQ and SQ processes in excited diatomic molecules in diatomic bath gases has also been demonstrated by the author and co-workers in a range of gas mixtures, [1][2][3][4][5][6][7]30 using the computational method to follow gas ensemble equilibration. The principal emphasis in the current study is on the comparison between the time-and quantum state-resolved data reported by ALDS and predictions obtained using the computational/theoretical model developed by the author and co-workers [13][14][15][16][17] as a means of validating the latter.…”

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

confidence: 99%

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

McCaffery

2016

The Journal of Chemical Physics

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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

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

confidence: 99%

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

McCaffery

2016

The Journal of Chemical Physics

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“…In fact Saigusa and Lim TM have recently argued that data from isoquinoline fluorescence in "cool" and "cold" beams provides evidence for such rotational level contributions to IVR. The possible role of vibration-rotation coupling in IVR has also been discussed 5 in connection with room temperature fluorescence data concerning p-difluorobenzene and p-fluorotoluene.…”

Section: Vibration-rotation Coupling As a Source Of Level Density Formentioning

confidence: 99%

“…Consequently the issue of IVR was not pursued seriously in the early SVL fluorescence studies, although subsequent developments have shown that the TIB and IVR contributions to congestion in room temperature fluorescence can be separated. [3][4][5][6] The first truly convincing arguments pointing to IVR as the cause of congestion were instead derived from SVL fluorescence spectra from molecules in cold supersonic beams where TIB is largely suppressed. Examples can be found in representative early papers of Levy and co-workers, 7 of Smalley and co-workers, 8 and of Amirav, Even and Jortner.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Vibrational Redistribution at Low State Densities in S₁ Aromatics. Evidence for Rotational Contributions

et al. 1983

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Evidence is presented concerning the onset of intramolecular vibrational redistribution (IVR) as one climbs the vibrational manifold of room temperature S1 aromatics. The onsets of IVR occur at S1 vibrational energies between 670 and 2000 cm−1 for various single and double ring aromatic molecules. The vibrational level densities in the onset region seem too small to support the extensive IVR that is observed in every molecule. Comparisons of room temperature fluorescence spectra with cold supersonic beam spectra from p-difluorobenzene support the proposition that Coriolis vibration–rotation coupling makes important contributions to the effective density of states in room temperature IVR.

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“…[1][2][3][4][5][6][7][8][9] The time resolved observation of IVR is of particular interest, and experimentally most convenient, for vibrational levels in electronically excited states, where the initial level can be prepared by impulsive laser excitation and where temporal evolution can be followed by fluorescence. 1'3'4'8'9 An interesting example of such experiments, concerned with IVR in the lowest excited singlet state of isolated anthracene molecules, has been reported by Zewail et al.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Vibrational Relaxation in Electronically Excited States

Voltz¹,

Boeglin²,

Villaeys³

et al. 1983

Laser Chemistry

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A density matrix approach for describing intramolecular dynamics, with special application to vibrational relaxation in excited electronic states, is presented. We derive the master equations governing intramolecular transfer of excitation energy between the states in a zeroth-order basis defined by considering the excitation and detection conditions in the time-resolved experiments. It is shown that, in this formalism, the memory function plays a central role. We note that the form of intramolecular memory is determined by the importance of quantum mechanical mixing of the zeroth-order states. A distinction is made between the subsystems of states with strong and weak mixing properties; while the former account for quasiperiodic character of coherent motion, the latter display a Markovian behavior. The physical conditions fixing the relative importance of quasiperiodic and statistical dynamics in individual systems are discussed. In the application to time resolved intramolecular vibrational relaxation, special consideration is given to the nature of the initially excited doorway states and the intermode couplings. The symmetry restrictions and the possible role of rotational motion in vibrational relaxation are also discussed, before considering the recent results obtained by Zewail et al. with anthracene in the first excited singlet state.

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Vibrational energy flow within excited electronic states of large molecules

Cited by 190 publications

References 6 publications

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

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

Intramolecular Vibrational Redistribution at Low State Densities in S₁ Aromatics. Evidence for Rotational Contributions

Intramolecular Vibrational Relaxation in Electronically Excited States

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Vibrational energy flow within excited electronic states of large molecules

Cited by 190 publications

References 6 publications

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

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

Intramolecular Vibrational Redistribution at Low State Densities in S1 Aromatics. Evidence for Rotational Contributions

Intramolecular Vibrational Relaxation in Electronically Excited States

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Intramolecular Vibrational Redistribution at Low State Densities in S₁ Aromatics. Evidence for Rotational Contributions