Two-step photoionization of trans-stilbene in acetonitrile via an ion-pair precursor studied with picosecond time-resolved absorption and Raman spectroscopies

► Picosecond time-resolved visible absorption and Raman spectra of trans-stilbene in acetonitrile have been measured. ► The newly found 440 nm absorption band and the 1599 cm−1 Raman band are assigned to a precursor of the radical cation. ► Precursor may well be an ion pair that holds an ejected electron.