Quantum dynamics of overtone relaxation in 30-mode benzene: A time-dependent local mode analysis for CH(ν=2)

Minehardt, Todd J.; Adcock, J.David; Wyatt, Róbert E.

doi:10.1063/1.478198

Cited by 22 publications

(9 citation statements)

References 48 publications

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“…Ideally, one would like to be able to reliably predict the rate and extent of IVR for a given molecule and a given method of excitation, starting from a small number of molecular parameters. Recent theoretical models have been able ͑starting from semiempirical potential energy surfaces͒ to successfully reproduce the experimentally observed data in molecules as large as benzene [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] and (CH 3 ) 3 CCCH 17 with densities of states in some cases in excess of 10 7 /cm Ϫ1 . To what extent is the knowledge gained about these specific molecules transferable to ''similar'' molecules, and how can the similarity be quantified?…”

Section: B Current Issuesmentioning

confidence: 99%

Intramolecular vibrational redistribution in aromatic molecules. I. Eigenstate resolved CH stretch first overtone spectra of benzene

Callegari

Merker

Engels

et al. 2000

The Journal of Chemical Physics

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We have used infrared-infrared double resonance spectroscopy to record a rovibrational eigenstate resolved spectrum of benzene in the region of the CH stretch first overtone. This experiment is the first of a series aimed at investigating intramolecular vibrational energy redistribution ͑IVR͒ in aromatic molecules. The experiment has been carried out in a supersonic molecular beam apparatus using bolometric detection. A tunable resonant cavity was used to enhance the on-beam intensity of the 1.5 m color center laser used to pump the overtone, and a fixed frequency ͓R(30)͔ 13 CO 2 laser was used to saturate the coinciding 18 r Q(2) transition of benzene. After assigning the measured lines of the highly IVR fractionated spectrum to their respective rotational quantum number J, analysis of the data reveals that the dynamics occurs on several distinct time scales and is dominated by anharmonic coupling with little contribution from Coriolis coupling. After the fast ͑ϳ100 fs͒ redistribution of the energy among the previously observed ''early time resonances'' ͓R. H.

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Section: B Current Issuesmentioning

confidence: 99%

Intramolecular vibrational redistribution in aromatic molecules. I. Eigenstate resolved CH stretch first overtone spectra of benzene

Callegari

Merker

Engels

et al. 2000

The Journal of Chemical Physics

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“…Previous studies of benzene spectra at high resolution showed that the energy after C-H stretch overtone excitation is rapidly redistributed among a first tier of states within 100-200 fs. Dynamical calculations indicate that mainly high frequency modes containing pronounced in-plane C-H wagging and out-of-plane C-H bend character are responsible for this fast process [26,27]. Then, in a second, slower step taking 10-20 ps or even longer, further redistribution occurs into the low frequency ring modes of the molecule thus producing the linewidths and spectral features observed by Nicholson and Lawrance [18] and others [15].…”

Section: Resultsmentioning

confidence: 83%

Intramolecular vibrational energy redistribution and intermolecular energy transfer of benzene in supercritical CO2: measurements from the gas phase up to liquid densities

Benten

Charvát

Link

et al. 2004

Chemical Physics Letters

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Femtosecond pump probe spectroscopy was employed to measure intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) of benzene in the gas phase and in supercritical (sc) CO 2. We observe two IVR time scales the faster of which proceeds within s ð1Þ IVR < 0:5 ps. The slower IVR component has a time constant of s ð2Þ IVR ¼ ð48 AE 5Þ ps in the gas phase and in scCO 2 is accelerated by interactions with the solvent. At the highest CO 2 density it is reduced to s ð2Þ IVR ¼ ð6 AE 1Þ ps. The corresponding IVR rate constants show a similar density dependence as the VET rate constants. Model calculations suggest that both quantities correlate with the local CO 2 density in the immediate surrounding of the benzene molecule.

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“…An additional step here was an ab initio calculation of the potential-energy surface. Papers [274,275] are representative examples (see also references cited therein and in review [130]). …”

Section: Theorymentioning

confidence: 99%

Intramolecular vibrational redistribution: from high-resolution spectra to real-time dynamics

2012

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Intramolecular vibrational redistribution is a fundamental phenomenon observed in polyatomic molecules when sufficiently excited vibrationally. In this paper, results mostly from the last two decades of research on this subject are summarized, obtained either from infrared spectroscopy with a resolution of as high as 10 À4 cm ÀI or, in a different approach, by using various pump-probe schemes with a temporal resolution from dozens of picoseconds to subpicoseconds.A A Makarov, A L Malinovsky, E A Ryabov

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Quantum dynamics of overtone relaxation in 30-mode benzene: A time-dependent local mode analysis for CH(ν=2)

Cited by 22 publications

References 48 publications

Intramolecular vibrational redistribution in aromatic molecules. I. Eigenstate resolved CH stretch first overtone spectra of benzene

Intramolecular vibrational redistribution in aromatic molecules. I. Eigenstate resolved CH stretch first overtone spectra of benzene

Intramolecular vibrational energy redistribution and intermolecular energy transfer of benzene in supercritical CO2: measurements from the gas phase up to liquid densities

Intramolecular vibrational redistribution: from high-resolution spectra to real-time dynamics

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