Spin and bonding properties and optical spectra of octahedral transition metal complexes using the multiple scattering X α method
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We have studied by the methods of picosecond spectroscopy the fluorescence risetimes of the S-4Sc and S2→S0 emissions of ρ -dimethylaminobenzonitrile in several polar solvents of increasing viscosity at 25 and -78°C to determine the relaxation dynamics controlling their kinetics. Vibronic relaxation resulting from interaction with the solvent as a dissipative medium appears to precede the S1-S0 fluorescence. An earlier hypothesis that the S2→+S0 emission follows a modified Debye theory of viscosity-controlled solvent reorganization is not completely supported by our data, though solvent viscosity does appear to influence the relaxation dynamics. Available data do not distinguish between intramolecular -N(CH3)2 rotation and nonviscosity limited solvent reorganization as leading to S2-S 0 emission, whose decay lifetime was determined to be ∼1 nsec.
author list (cited authors)
Larsson, S., & Connolly, J.