Abstract
Femtosecond broad-band pump−probe spectroscopy has been used to study intramolecular bichromophoric coupling and structural relaxation in pyrene and aryl pyrene derivatives in solution. The influence of aryl substituents on the S2 → S1 internal conversion process, which occurs with a time constant of ∼75 fs in pyrene, has been investigated. While in 1-phenylpyrene the internal conversion is faster than 50 fs, it is slower in 1-biphenyl-4-yl-pyrene (105 fs). The temporal evolution of the transient absorption spectrum indicates strong mixing of several “zero-order” electronic configurationswhich evolve separately with timein the S1 and the S2 states. The time-resolved spectra are interpreted within the framework of an adiabatic state model which includes interchromophoric electronic coupling. In this paper we give a full description of the experimental setup, the data acquisition procedure, and several experimental details about the characterization of the broad-band femtosecond white light source.
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