The spectroscopy and photochemistry of quinioline structural isomers: (E)- and (Z)-phenylvinylnitrile.

In Titan's atmosphere, photochemical pathways that lead to nitrogen heteroaromatics may incorporate photoisomerization of their structural isomers as a final step. (E)- and (Z)-phenylvinylnitrile ((E)- and (Z)-PVN, C6H5-CH=CHCN) are structural isomers of quinoline that themselves possess extensive absorptions in the ultraviolet, and thus may engage in such photoisomerization pathways. The present study explores the vibronic spectroscopy and photo-induced isomerization of gas-phase (E)- and (Z)-PVN in the 33,600-35,850 cm(-1) region under jet-cooled conditions. The S0-S1 origins for (E)- and (Z)-PVN have been identified at 33 827 cm(-1) and 33 707 cm(-1), respectively. Isomer-specific UV-UV hole-burning and UV depletion spectra reveal sharp vibronic structure that extends over almost 2000 cm(-1), with thresholds for fast non-radiative decay identified by a comparison between hole-burning and UV depletion spectra. Dispersed fluorescence spectra of the two isomers enable the assignment of many low frequency transitions in both molecules, aided by harmonic frequency calculations (B3LYP/6-311++G(d,p)) and a comparison with the established spectroscopy of phenylvinylacetylene, the ethynyl counterpart to PVN. Both isomers are proven to be planar in both the S0 ground and S1 electronic excited states. (E)-PVN exhibits extensive Duschinsky mixing involving out-of-plane modes whose frequencies and character change significantly in the ππ* transition, which modulates the degree of single- and double-bond character along the vinylnitrile substituent. This same mixing is much less evident in (Z)-PVN. The spectroscopic characterization of (E)- and (Z)-PVN served as the basis for photoisomerization experiments using ultraviolet hole-filling spectroscopy carried out in a reaction tube affixed to the pulsed valve. Successful interconversion between (E) and (Z)-PVN was demonstrated via ultraviolet hole-filling experiments. Photoexcitation of (E)- and (Z)-PVN at their respective S0-S1 origins failed to produce quinoline, a simple polycyclic aromatic nitrogen heterocylcle, within the detection sensitivity of our experiments. Stationary points along the potential energy surface associated with (Z)-PVN → quinoline isomerization showed a barrier of 93 kcal/mol associated with the first step in the isomerization process, slowing the interconversion process at the excitation energies used (96 kcal/mol) to timescales beyond those probed in the present experiment.