Excited state vibrational dynamics of 4-ethylaniline (X)1 clusters (X = Ar, N2, and CH4)

Article abstract of DOI:10.1063/1.464187

Intracluster vibrational redistribution (IVR) and vibrational redissociation (VP) dynamics of 4-ethylaniline (Ar)₁, (N2)₁, and (CH4)₁ clusters have been studied by time-correlated single photon counting, mass-resolved excitation spectroscopy, and dispersed emission spectroscopy.The 4-ethylaniline molecule has a low frequency ethyl group torsion vibrational mode, which is similar in energy to the van der Waals modes of the clusters.This mode, because of its low energy (ca. 35 cm^-1), plays a role in the vibrational dynamics of the clusters studied.The cluster dissociation rates and product state distributions can be modeled by a serial IVR/VP mechanism for which the VP step is treated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory.The resulting agreement between the calculated and experimental rates and product state intensities indicates that a statistical distribution of energy among all low frequency modes exists for 4-ethylaniline/polyatomic solvent clusters in which k_IVR<*>k_VP.For 4-ethylaniline (Ar)₁ clusters k_VP > k_IVR and a statistical distribution of energy among the chromophore and van der Waals modes is not achieved.The central determining factor for the vibrational dynamics of these clusters is overall density of low energy modes.

Full text of DOI:10.1063/1.464187

Excited state vibrational dynamics of 4ethylaniline (X)1 clusters (X=Ar, N2, and
CH4)
Max F. Hineman, Elliot R. Bernstein, and David F. Kelley
Citation: The Journal of Chemical Physics 98, 2516 (1993); doi: 10.1063/1.464187
View online: http://dx.doi.org/10.1063/1.464187
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/98/4?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
134.176.129.147 On: Mon, 15 Dec 2014 10:14:10