First comparison of vibrational relaxation in ground and excited electronic states of polyatomic molecules. S0 and S1 p-difluorobenzene

Muller, D.; Lawrance, Warren D.; Knight, Alan

doi:10.1021/j150642a037

Cited by 23 publications

(7 citation statements)

References 3 publications

(3 reference statements)

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“…The sequence spacings, Ј-Љ, measured by TP and HLMR, are listed in Table 5 in order of increasing S 0 frequency (and therefore in decreasing Boltzmann population). Two of the predicted sequence spacings, for 16 and 20 , are not as close to the observed as might be expected; this discrepancy is probably due to anharmonicity (see below). These sequences have gone unassigned previously; however, using the data in Table 1, the sequence spacings for the low-frequency vibrations can be predicted and have been included in Table 5.…”

Section: Sequencesmentioning

confidence: 74%

TheS1(1A1)–S0(1A1) Electronic Transition of Jet-Cooledo-Difluorobenzene

Swinn

Kable

1998

Journal of Molecular Spectroscopy

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Section: Sequencesmentioning

confidence: 74%

TheS1(1A1)–S0(1A1) Electronic Transition of Jet-Cooledo-Difluorobenzene

Swinn

Kable

1998

Journal of Molecular Spectroscopy

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“…The best comment on the S 0 vs S 1 question comes from an ensemble of tour-de-force VET studies of selected S 0 levels of p -difluorobenzene. Using stimulated emission pumping (SEP) to populate various S 0 levels in both 300 K and cold jet experiments (see below), abundant energy transfer data emerged that may be compared with S 1 experiments. − The behavior in S 0 and S 1 states is similar in all respects.…”

Section: State-to-state Vibrational Energy Transfer Within Excited El...mentioning

confidence: 99%

“…Using stimulated emission pumping (SEP) to populate various S 0 levels in both 300 K and cold jet experiments (see below), abundant energy transfer data emerged that may be compared with S 1 experiments. [195][196][197][198][199] The behavior in S 0 and S 1 states is similar in all respects.…”

Section: State-to-state Vibrational Energy Transfer Within Excited El...mentioning

confidence: 99%

Vibrational Energy Transfer

1996

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Many aspects of the collision dynamics of vibrational energy transfer are presented. Special emphasis is placed on three broad areas within this field: (1) vibrational energy transfer in large molecules (>10 modes) at low excitation, (2) vibrational energy transfer in large molecules at high vibrational excitation, and (3) vibrational energy transfer of highly excited small molecules. Advances in laser methods have revolutionized experimental investigations of all of these areas. Recent results are presented, and directions for the future are discussed.

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“…The addition of extra modes in a vibrational description has been observed to increase the vibrational relaxation rate substantially. (See, for example, levels 5 2 30 2 and 3 1 5 2 30 2 in S 0 pDFB 30 or the addition of a single quantum of ν 30 to any S 1 vibrational description of pDFB 46 in the next section.) The experimental value of the rate coefficient for 6 1 16 1 therefore may be somewhat high on the basis of these earlier precedents.…”

Section: B Vibrational-state Dependence Of K Imentioning

confidence: 99%

Semiempirical Model of Vibrational Relaxation for Estimating Absolute Rate Coefficients

Kable

Knight

2003

J. Phys. Chem. A

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A semiempirical theoretical model is developed for estimating the rates of collision-induced V-T vibrational relaxation from an initially excited vibrational state in a polyatomic molecule to a relatively dense field of destination vibrational states. The rationale has been to provide a means of estimating absolute relaxation rate coefficients, with a reasonable level of precision, for relaxation induced by a wide range of collision partners (atomic, diatomic, and polyatomic) and for a relatively wide range of temperatures. The model is based on calculating an efficiency P for the vibrational relaxation process by making use of relevant known molecular and intermolecular parameters. The inelastic rate coefficient for vibrational relaxation then emerges from a product of this efficiency and the classical Lennard-Jones elastic encounter rate. A feature of the model is that it uses no adjustable parameters. Comparisons are made between the predictions from the model and a number of experimental measurements of specific dependencies of vibrational relaxation rate coefficients (e.g. on collision partner properties, on the initial vibrational state, and on temperature) to characterize and illustrate the ingredients that deliver the estimate for P. A correlation between the predictions of the model and data from over 100 experimental systems and for a temperature range from 2-300 K invites the conclusion that the model is useful for estimating the absolute magnitude of state-to-field vibrational relaxation rate coefficients in the intermediate regime of final state densities to within an overall accuracy of 30% and with an average error of -10%.

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First comparison of vibrational relaxation in ground and excited electronic states of polyatomic molecules. S0 and S1 p-difluorobenzene

Cited by 23 publications

References 3 publications

TheS1(1A1)–S0(1A1) Electronic Transition of Jet-Cooledo-Difluorobenzene

TheS1(1A1)–S0(1A1) Electronic Transition of Jet-Cooledo-Difluorobenzene

Vibrational Energy Transfer

Semiempirical Model of Vibrational Relaxation for Estimating Absolute Rate Coefficients

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