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Pump-degenerate four wave mixing as a technique for analyzing structural and electronic evolution: multidimensional time-resolved dynamics near a conical intersection.

Pump-degenerate four wave mixing (pump-DFWM) is used to simultaneously study the early events in structural and electronic population dynamics of the non-adiabatic passage between two excited electronic states. After the precursor state S2 is populated by an initial pump beam, a DFWM sequence is set resonant with the S1 --> Sn transition on the successor state S1. The information obtained by pump-DFWM is two-fold: by scanning the delay between the initial pump and the DFWM sequence, the evolution of the individual excited-state modes is observed with a temporal resolution of 20 fs and a spectral resolution of 10 cm-1. Additionally, pump-DFWM yields information on electronic population dynamics, resulting in a comprehensive description of the S2 --> S1 internal conversion. As a system in which the interplay between structural and electronic evolution is of great interest, all-trans-beta-carotene in solution was chosen. The pump-DFWM signal is analyzed for different detection wavelengths, yielding results on the ultrafast dynamics between 1Bu+ (S2) and 2Ag- (S1). The process of vibrational cooling on S1 is discussed in detail. Furthermore, a low-lying vibrationally hot state is excited and characterized in its spectroscopic properties. The combination of highly resolved vibrational dynamics and simultaneously detected ultrafast electronic state spectroscopy gives a complete picture of the dynamics near a conical intersection. Because pump-DFWM is a pure time domain technique, it offers the prospect of coherent control of excited-state dynamics on an ultrafast time scale.