Trans-stilbene in n-hexane is excited with excess vibrational energy in the range 0-7000 cm~(-1). In the excited electronic state, the Raman linewidth of the ethylenic C=C stretching mode at 1570 cm~(-1) is followed with ~100 fs time resolution. Upon excitation with substantial excess energy, the width of the peak is initially broad and then narrows within a few picoseconds, as observed previously by Iwata and Hamaguchi [Chem. Phys. Lett. 196, 462 (1992)]. This narrowing is understood as being caused by cooling of the initially hot molecule, by the surrounding solvent. In this Communication, we report that upon excitation without excess energy, the width is initially relatively narrow and then broadens on a picosecond time scale. The broadening is attributed to heating of the molecule by solvent collisions. It follows that the nascent population in the excited electronic state is cold as compared with the solvent. Such reduction of the initial vibrational energy may affect the rate for the subsequent photoreaction, especially in the absence of the solvent.
展开▼
