The two-photon excitation spectrum of fluorobenzene vapor

The two-photon excitation spectrum of fluorobenzene vapor has been recorded in the region of the $\text{A}\text{?}{}^1\text{B}{}_2\text{←}\text{X}\text{?}{}^1\text{A}{}_1$ transition. The spectrum shows considerable rovibronic structure with the bulk of the intensity lying in the subsystem induced by the ν₁₄(b₂) vibration. Two types of rovibronic contours, arising from ΔK_a = ±1 and from ΔK_a = 0, ±2 transitions, are identified. Major features in these contours are assigned by comparison with synthetic spectra, calculated using known upper and lower state rotational constants. The intensity distribution among the various bands in progressions of the totally symmetric vibrations is considerably different from that in the one-photon absorption spectrum, and the possible reasons for this are discussed.