Electronic Spectroscopy of cis- and trans-meta-Vinylbenzyl Radicals.

The D0(2A″)-D1(2A″) electronic transition of resonance-stabilized radical C9H9 isomers cis- and trans-meta-vinylbenzyl (MVB) has been investigated using resonant two-color two-photon ionization (R2C2PI) and laser-induced fluorescence. The radicals were produced in a discharge of m-vinyltoluene diluted in Ar and probed under jet-cooled conditions. The origin bands of the cis and trans conformers are at 19 037 and 18 939 cm-1, respectively. Adiabatic ionization energies near 7.17 eV were determined for both conformers from two-color ion-yield scans. Dispersed fluorescence (DF) was used to conclusively identify the cis-conformer: ground-state cis-MVB eigenvalues calculated for a Fourier series fit of a computed vinyl torsion potential are in excellent agreement with torsional transitions in the 19 037 cm-1 DF spectrum. R2C2PI features arising from cis- or trans-MVB were distinguished by optical-optical hole-burning spectroscopy and vibronic assignments were made with guidance from density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. There is a notable absence of mirror symmetry between excitation and emission spectra for several totally symmetric modes, whereby modes that are conspicuous in emission are nearly absent in excitation, and vice versa. This effect is largely ascribed to interference between Franck-Condon and Herzberg-Teller contributions to the electronic transition moment, and its pervasiveness a consequence of the low symmetry (Cs) of the molecule, which permits intensity borrowing from several relatively bright electronic states of A″ symmetry.