The A?1B2-X?1A1 two-photon fluorescence excitation spectrum of 1,3-difluorobenzene

The $\text{A}\text{?}{}^1\text{B}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ system of 1,3-difluorobenzene has been observed using the technique of two-photon fluorescence excitation obtained with a pulsed dye laser. Calibration was achieved by a combination of the neon optogalvanic spectrum and etalon fringes. In circular, compared to linear, polarization the bands divide into two groups, those which are B₂-A₁ and which retain their intensity with circular polarization, and those which are A₁-A₁ and lose about 60% of their intensity under the same conditions. These two kinds of bands also show characteristic rotational contours. All of the A₁-A₁ bands whose assignments are established obtain their intensity through vibronic interaction in which the vibration ν′₂₅ (ν′₁₄ in the Wilson numbering) mixes the $\text{A}\text{?}$ with, presumably, the $\text{X}\text{?}$ state. There is an important Fermi resonance between the 9¹ and 10¹11¹ levels. Parts of the one-photon absorption spectrum have been photographed to identify sequences associated with the 0₀⁰ band for comparison with those observed in the two-photon spectrum, and to search for bands involving odd quanta of b₂ vibrations, including ν′₂₅ (ν′₁₄); none was found.