Abstract
The vibronic spectroscopy of ortho-, meta-, and para-diethynylbenzene (oDEB, mDEB, and pDEB) was studied by two-color resonant two photon ionization (R2PI). The symmetry allowed S0−S1 origins of oDEB, mDEB, and pDEB were located at 33 515, 33 806, and 34 255 cm-1, respectively, with the vibronic structure extending about 2000 cm-1 above the origin in oDEB and mDEB, but more than 3000 cm-1 in pDEB. Major peaks in each spectrum were attributed to vibronically induced bands, indicating strong coupling of the S1 state to the S2 state. Ground-state infrared spectra in the C−H stretch region (3000−3360 cm-1) were obtained using resonant ion-dip infrared spectroscopy (RIDIRS). In all three isomers, the acetylenic C−H stretch fundamental was split by Fermi resonance with a combination band composed of the C⋮C stretch and two quanta of the C⋮CH bend. This Fermi resonance was detuned in the overtone region of pDEB, which showed a single peak at 6556 cm-1. Infrared spectra were also recorded in the excited electroni...
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