Solvent reorganization around a "giant dipole" molecule

W. S. Struve*, P. M. Rentzepis, Joshua Jortner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The fluorescence risetimes of the 1La and 1Lb excited states of p -dimethylaminobenzonitrile (DMAB) in ethanol and methylcyclohexane following irradiation at room temperature by the fourth harmonic (2650 A) of a Nd3 + glass laser were measured directly using picosecond spectroscopy. The onset of !L b fluorescence, governed by prior vibronic relaxation in both polar and nonpolar solvents, occurs within 7-20 psec after the exciting pulse. The 1L a fluorescence, characterized by a noticeably longer risetime of 40 psec at room temperature, yields directly the solvent orientational relaxation time in the field of the '£ state's large dipole moment (23 D). This measured relaxation time is consistent with a modification of the Debye theory of viscosity-limited solvent reorganization.

Original languageEnglish
Pages (from-to)5020-5041
Number of pages22
JournalThe Journal of Chemical Physics
Volume59
Issue number9
DOIs
StatePublished - 1973
Externally publishedYes

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