Abstract
Femtosecond transient absorption spectroscopy of transition states has recently been applied to the study of both Tl-halide1 and Bi22 gas-phase photodissocation. In our approach a femtosecond UV pump source excites a molecule to a repulsive electronic state, V0(R). After a variable delay, a femtosecond probe pulse is applied. In this case, the probe pulse is an ~10000 cm–1 wide white-light continuum pulse, and the photofragments are detected by means of broadband absorption spectroscopy. A complete spectrum corresponding to a given pump-probe delay is thus recorded in a single shot. Changes that are observed in the absorption spectrum as a function of the pump-probe delay provide information about variations δω (R) in the separation between the potential curves, V0(R) and V1(R), involved in the probe transition occurring as the interatomic spacing, R, is varied. These time-dependent absorption spectra form the data base for this approach to real-time transition-state spectroscopy.
© 1990 Optical Society of America
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