Perpendicular State of an Electronically Excited Stilbene: Observation by Femtosecond-Stimulated Raman Spectroscopy

J Phys Chem Lett. 2016 Oct 20;7(20):4047-4052. doi: 10.1021/acs.jpclett.6b01923. Epub 2016 Sep 30.

Abstract

In the photoisomerization path of stilbene, a perpendicular state P on the S1 potential energy surface is expected just before internal conversion through a conical intersection S1/S0. For decades the observation of P was thwarted by a short lifetime τP in combination with slow population flow over a barrier. But these limitations can be overcome by ethylenic substitution. Following optical excitation of trans-1,1'-dicyanostilbene, P is populated significantly (τP = 27 ps in n-hexane) and monitored by an exited-state absorption band at 370 nm. Here we report stimulated Raman lines of P. The strongest, at 1558 cm-1, is attributed to stretching vibrations of the phenyl rings. Transient electronic states, resonance conditions, and corresponding Raman signals are discussed.