Journal of Physical Chemistry, Vol.99, No.13, 4380-4385, 1995
Transient States of an Intramolecular Proton-Transfer Cycle Studied by Degenerate 4-Wave-Mixing
The kinetics of an intramolecular proton transfer cycle, in particular the population of the various transient states, is investigated by a new experimental technique : degenerate four-wave mixing in combination with excitation of the molecules by picosecond (2 x 10(-11) s) UV pulses. The molecular hyperpolarizability gamma((3)) of different excited electronic states is measured at five spectral positions between 10 000 and 30 000 cm(-1). Resonance enhancement up to 3 orders of magnitude near electronic transitions is observed. The high sensitivity of gamma((3)) to molecular resonances allows the study of extremely short-lived states. As an example, data are presented on the dynamics of the intramolecular proton transfer reaction in 2-(2’-hydroxyphenyl)benzothiazole where three transient states are elucidated.
Keywords:3RD-HARMONIC GENERATION;ROTATIONAL DIFFUSION;SINGLE-BEAM;SPECTROSCOPY;2-(2’-HYDROXYPHENYL)BENZOTHIAZOLE;2-(2-HYDROXYPHENYL)BENZOTHIAZOLE;FEMTOSECOND