Bound orbiting states of benzene–Ar and evidence for reversible intramolecular vibrational energy redistribution within the complex

Sampson, Rebecca K; Lawrance, Warren D.

doi:10.1016/j.cplett.2004.11.097

Cited by 5 publications

(3 citation statements)

References 17 publications

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“…5,27,46 The IVR process that is a precursor to dissociation provides energy to the van der Waals modes, allowing the complex to access bound orbiting states. Calculations show that the barrier to bound orbiting states is well below the dissociation energy.…”

Section: Figmentioning

confidence: 99%

Recoil energy distributions for dissociation of the van der Waals molecule p-difluorobenzene–Ar with 450–3000cm−1 excess energy

Bellm

Lawrance

2005

The Journal of Chemical Physics

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Velocity map imaging has been used to measure the distributions of translational energy released in the dissociation of p-difluorobenzene-Ar van der Waals complexes from the 5 1 , 3 1 , 5 2 , 3 1 5 1 , 5 3 , 3 2 , and 3 2 5 1 states. These states span 818-3317 cm −1 of vibrational energy and correspond to a range of energies above dissociation of 451-2950 cm −1 . The translational energy release ͑recoil energy͒ distributions are remarkably similar, peaking at very low energy ͑10-20 cm −1 ͒ and decaying in an exponential fashion to approach zero near 300 cm −1 . The average translational energy released is small, shows no dependence on the initial vibrational energy, and spans the range 58-72 cm −1 for the vibrational levels probed. The average value for the seven levels studied is 63 cm −1 . The low fraction of transfer to translation is qualitatively in accord with Ewing's momentum gap model ͓G. E. Ewing, Faraday Discuss. 73, 325 ͑1982͔͒. No evidence is found in the distributions for a high energy tail, although it is likely that the experiment is not sufficiently sensitive to detect a low fraction of transfer at high translational energies. The average translational energy released is lower than has been seen in comparable systems dissociating from triplet and cation states.

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Section: Figmentioning

confidence: 99%

Recoil energy distributions for dissociation of the van der Waals molecule p-difluorobenzene–Ar with 450–3000cm−1 excess energy

Bellm

Lawrance

2005

The Journal of Chemical Physics

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“…The vibrational relaxation has been widely studied experimentally and theoretically because of its fundamental importance in chemistry. , In the condensed phase, a large number of studies have been reported on the intramolecular vibrational relaxation (IVR) and intermolecular vibrational energy transfer (VET) by using various time-resolved pump−probe techniques with ultrashort laser pulses. − According to these extensive works, it is widely established that the energy put into the high-frequency vibrational level such as OH and CH stretches is first redistributed within the molecule in a few picoseconds, and the energy is further redistributed into the surrounding molecules. In parallel, a large number of studies on the vibrational relaxation have been reported for gas-phase molecules and clusters. ,− A major target of the studies on molecular clusters is to elucidate precisely the energy dissipation routes and obtain each rate constant from the knowledge of the anharmonic coupling, the density of states of bath mode, and the relative orientation between solute and solvent molecules. Among many works, we have been studying the dynamics of the X−H stretching vibration, where X refers to O, C, or N atom, of isolated molecules as well as their clusters in S 0 by means of picosecond IR−UV pump−probe spectroscopy. − …”

Section: Introductionmentioning

confidence: 99%

“…In parallel, a large number of studies on the vibrational relaxation have been reported for gas-phase molecules and clusters. 3,[14][15][16][17][18][19][20][21] A major target of the studies on molecular clusters is to elucidate precisely the energy dissipation routes and obtain each rate constant from the knowledge of the anharmonic coupling, the density of states of bath mode, and the relative orientation between solute and solvent molecules. Among many works, we have been studying the dynamics of the X-H stretching vibration, where X refers to O, C, or N atom, of isolated molecules as well as their clusters in S 0 by means of picosecond IR-UV pump-probe spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Picosecond IR−UV Pump−Probe Study on the Vibrational Relaxation of Phenol−Ethylene Hydrogen-Bonded Cluster: Difference of Relaxation Route/Rate between the Donor and the Acceptor Site Excitations

et al. 2006

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Picosecond time-resolved IR-UV pump-probe spectroscopy has been performed to study intracluster vibrational energy redistribution (ICVR) and vibrational predissociation (VP) for the OH and CH stretch vibrations of phenol-ethylene hydrogen-bonded cluster. The transient UV spectra after the picosecond IR pulse excitation of these modes were observed by 1+1 REMPI via S(1) with a picosecond UV pulse. We have focused on the difference of the energy flow routes and their rates between the donor (phenol) and the acceptor (ethylene) site. Though the transient UV spectra showed a similar broad feature for all the vibrations examined, the time profiles exhibited a remarkable site dependence, as well as substantial mode dependence. Especially, we found a large difference in the early stage of the IVR evolution and the rates, whereas the VP rates were very similar.

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Vibrational predissociation in weakly-bound clusters: A dispersed fluorescence study of toluene rare-gas complexes

Campo

Mackenzie

2008

Chemical Physics Letters

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The vibrational predissociation (VP) dynamics of toluene-Ar and toluene-Ne complexes have been investigated using single vibronic level fluorescence spectroscopy. For several levels, comparison of the dispersed fluorescence spectra with those from monomer levels permits the identification of the final monomer vibrational level. Pumping of the low-lying S 1 1 0 1 0 1 0 25 24 13 / or 1 0 37 transitions in toluene-Ar, for example, gives rise to efficient VP leaving the resulting toluene monomer in its vibrationless S 1 state. By contrast, in the case of toluene-Ne, VP following 1 37 level pumping leaves the toluene molecule in an excited 1 16 level which is optically inaccessible from the ground state.

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Bound orbiting states of benzene–Ar and evidence for reversible intramolecular vibrational energy redistribution within the complex

Cited by 5 publications

References 17 publications

Recoil energy distributions for dissociation of the van der Waals molecule p-difluorobenzene–Ar with 450–3000cm−1 excess energy

Recoil energy distributions for dissociation of the van der Waals molecule p-difluorobenzene–Ar with 450–3000cm−1 excess energy

Picosecond IR−UV Pump−Probe Study on the Vibrational Relaxation of Phenol−Ethylene Hydrogen-Bonded Cluster: Difference of Relaxation Route/Rate between the Donor and the Acceptor Site Excitations

Vibrational predissociation in weakly-bound clusters: A dispersed fluorescence study of toluene rare-gas complexes

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