Solution dynamics by line shape analysis, resonance light scattering and femtosecond four-wave mixing

Erik T.J. Nibbering, Koos Duppen, Douwe A. Wiersma

OnderzoeksoutputAcademicpeer review

33 Citaten (Scopus)
230 Downloads (Pure)


The results of line shape analysis, resonance light scattering and femtosecond four-wave mixing measurements are reported on several organic molecules in solution. It is shown that a Brownian oscillator model for line broadening provides a full description for the optical dynamics in aprotic solutions. The dynamics of all systems studied is found to occur in the intermediate modulation regime, where the amplitude Δ and inverse correlation time Λ of the Brownian oscillator are about equal: Δ/Λ ≈ 1. Isotopic substitution of either probe or solvent is shown to have no effect on the dynamics, from which it is concluded that the vibrational force field plays a minor role in determining the line shape. Four-wave mixing experiments with chirped femtosecond pulses yield intense coherent Raman scattering signals due to ground and excited-state vibrational coherences which are very effectively driven by the two instantaneous light fields whose frequency difference matches exactly a vibrational mode. It is shown that the “chirped” four-wave mixing signal near zero delay time only mimics the two-pulse photon echo if the system dynamics fall in the fast modulation limit: Δ/Λ « 1. Otherwise this signal is damped not only by dephasing but also by solvation dynamics.
Originele taal-2English
Pagina's (van-tot)347-370
Aantal pagina's24
TijdschriftJournal of photochemistry and photobiology a-Chemistry
Nummer van het tijdschrift3
StatusPublished - 15-jan.-1992
Duur: 28-jul.-19912-aug.-1991

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