Probing E/Z isomerization on the C10H8 potential energy surface with ultraviolet population transfer spectroscopy

The excited-state dynamics of phenylvinylacetylene (1-phenyl-1-buten-3-yne, PVA) have been studied using laser-induced fluorescence spectroscopy, ultraviolet depletion spectroscopy, and the newly developed method of ultraviolet population transfer spectroscopy. Both isomers of PVA (E and Z) show a substantial loss in fluorescence intensity as a function of excitation energy. This loss in fluorescence was shown to be due to the turn-on of a nonradiative process by comparison of the laser-induced fluorescence spectrum to the ultraviolet depletion spectrum of each isomer, with a threshold 600 cm(-1) above the electronic origin in Z-PVA and 1000 cm(-1) above the electronic origin in E-PVA. Ab initio and density functional theory calculations have been used to show that the most likely source of the nonradiative process is from the interaction of the pi pi* state with a close lying pi sigma* state whose minimum energy structure is bent along the terminal CCH group. Ultraviolet population transfer spectroscopy has been used to probe the extent to which excited-state isomerization is facilitated by the interaction with the pi sigma* state. In ultraviolet population transfer spectroscopy, each isomer was selectively excited to vibronic levels in the S(1) state with energies above and below the threshold for fluorescence quenching. The ultraviolet-excited populations are then recooled to the zero point levels using a reaction tube designed to constrain the supersonic expansion and increase the collision cooling capacity of the expansion. The new isomeric distribution was detected in a downstream position using resonant-2-photon ionization spectroscopy. From these spectra, relative isomerization quantum yields were calculated as a function of excitation energy. While the fluorescence quantum yield drops by a factor of 50-100, the isomerization quantum yields remain essentially constant, implying that the nonradiative process does not directly involve isomerization. On this basis, we postulate that isomerization occurs on the ground-state potential energy surface after internal conversion. In these experiments, the isomerization to naphthalene was not observed, implying a competition between isomerization and cooling on the ground-state potential energy surface.