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Vibrational spectra and relaxation of benzonitrile and its clusters using time‐resolved stimulated Raman–UV double resonance spectroscopy
Author(s) -
Yamamoto Ryousuke,
Ishikawa Seiichi,
Ebata Takayuki,
Mikami Naohiko
Publication year - 2000
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/(sici)1097-4555(200004)31:4<295::aid-jrs542>3.0.co;2-y
Subject(s) - benzonitrile , raman spectroscopy , relaxation (psychology) , nuclear magnetic resonance , resonance (particle physics) , resonance raman spectroscopy , spectral line , spectroscopy , chemistry , molecular physics , materials science , atomic physics , optics , physics , organic chemistry , quantum mechanics , psychology , social psychology , astronomy
Raman spectra of ring‐breathing (ν 12 ) and CN stretching vibrations (ν CN ) of jet‐cooled benzonitrile and its clusters with Ar, H 2 O, CH 3 OH, CH 3 CN, CCl 4 , CHCl 3 and CHF 3 were observed by stimulated Raman–UV double resonance spectroscopy. Cluster structures were determined on the basis of the observed vibrational spectra, rotational contour analyses of the high resolution S 1 –S 0 electronic spectra and ab initio molecular orbital calculations with the HF/6–31G(d,p) basis set. It was found that the types of the cluster structures are classified into three groups. (1) The clusters with H 2 O, CH 3 OH and CH 3 CN represent the ‘side’‐type structure, in which the intermolecular bond is formed in the phenyl plane of benzonitrile, and the benzonitrile dimer also belongs to this structure. (2) The clusters with Ar and CCl 4 form the ‘on‐top’‐type structure, where Ar or CCl 4 is located above the phenyl plane. (3) The clusters with CHCl 3 and CHF 3 have the ‘linear’‐type structure, in which these molecules are located at the N end of the CN group of benzonitrile. The rate constants of the vibrational relaxation for these clusters occurring after the Raman excitation to their ν 12 vibrations were also observed. It was found that different rate constants are associated with the different types of cluster structures. That is, the 12 1 levels of the ‘side’‐type clusters relax much faster than those of other types of the clusters. The results represent a clear indication that the anharmonic coupling between ν 12 and intermolecular vibrations are much larger in the ‘side’‐type clusters than others. Copyright © 2000 John Wiley & Sons, Ltd.