Spectral broadening and diffusion by torsional motion in biphenyl

We have studied biphenyl by time-dependent density-functional theory. In particular, we have analyzed the dependence of singlet excitation energies and transition dipoles on the torsional angle between the phenyl groups. The torsional spectrum has been computed quantum mechanically as well as semicl...

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Bibliographic Details
Published in:The Journal of chemical physics 2005-10, Vol.123 (14), p.144311-144311-9
Main Authors: Beenken, Wichard J. D., Lischka, Hans
Format: Article
Language:English
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Summary:We have studied biphenyl by time-dependent density-functional theory. In particular, we have analyzed the dependence of singlet excitation energies and transition dipoles on the torsional angle between the phenyl groups. The torsional spectrum has been computed quantum mechanically as well as semiclassically in order to understand how this influences the broadening of absorption and luminescence spectra. Our results are in best agreement with supersonic jet spectroscopy data, but also fit astonishingly well to spectra of biphenyl in condensed phase. Furthermore, we compare the torsional and vibrational relaxation and discuss qualitatively the general consequences for poly- para -phenylenes and related conjugated polymers as poly-thiophenes, considering, in particular, how side chains and solvents may affect the optical spectra.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.2049269