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• W2068590199 abstract "The role of ring torsion in the enhancement of intramolecular vibrational energy redistribution (IVR) in aromatic molecules was investigated by conducting excitation and dispersed fluorescence spectroscopy of 1,1'-binaphthyl (1,1'-BN) and 2,2'-BN. The dispersed fluorescence spectra of 1,1'-BN in the origin region of S(1)-S(0) were well resolved, which presented 25-27 cm(-1) gaps of torsional mode in the ground state. The overall profile of the dispersed spectra of 1,1'-BN is similar to that of naphthalene. In contrast, the spectra of 2,2'-BN were not resolved due to the multitude of the active torsional modes. In both cases, dissipative IVR was observed to take place with a relatively small excess vibrational energy: 237.5 cm(-1) for 1,1'-BN and 658 cm(-1) for 2,2'-BN, which clearly shows that ring torsion efficiently enhances the IVR rate. Ab initio and density functional theory calculations with medium-sized basis sets showed that the torsional potential of 1,1'-BN has a very flat minimum over the range of torsional angles from ca. 60° to 120°, whereas that of 2,2'-BN showed two well-defined potential minima at ca. 40° and 140°, in resemblance to the case of biphenyl. In this work, we propose that aromatic molecules be classified into strong and weak torsional hindrance cases: molecules with strong hindrance case show shorter torsional progressions and more effective IVR dynamics than do those with weak hindrance." @default.
• W2068590199 created "2016-06-24" @default.
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• W2068590199 date "2012-01-01" @default.
• W2068590199 modified "2023-10-03" @default.
• W2068590199 title "Effect of ring torsion on intramolecular vibrational redistribution dynamics of 1,1′-binaphthyl and 2,2′-binaphthyl" @default.
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• W2068590199 doi "https://doi.org/10.1039/c1cp22854d" @default.
• W2068590199 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/22124335" @default.
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