S nS1 and S1→S resonance CARS spectra of perylene in the S1 state

Abstract
Resonance CARS spectrum of perylene in the first excited singlet (S1 ) state was observed in solution at room temperature. The observed shifts of Raman frequencies from the ground (S0 ) state values were related to the results of the PPP‐SCF‐CI MO calculation and the normal coordinate calculation. The experiment, intended to observe the resonance CARS signal of the S0 state, was found to give the signal predominated by the lines of the S1 state. It was also concluded that the peculiar feature originating from the simultaneous role of the pump beam depleted the molecules in the S0 state, populated the S1 state, and caused the resonance effect on CARS through the intense S1S0 transition.

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