Revealing Long-Range Substituent Effects in the Laser-Induced Fluorescence and Dispersed Fluorescence Spectra of Jet-Cooled CH x F 3- x CH 2 O ( x = 1, 2, 3) Radicals

The B̃-X̃ laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the atmospherically important β-monofluoro ethoxy (MFEO), β,β-difluoro ethoxy (DFEO), and β,β,β-trifluoro ethoxy (TFEO) radicals were recorded with vibronic resolution under jet-cooled conditions. To simulate the spectra, Franck-Condon factors were obtained from quantum chemical computations carried out at the CAM-B3LYP/6-311++G(d,p) level of theory. The simulations reproduce well both the LIF and DF spectra. Both conformers (G and T) of MFEO and one (G) of the two conformers of DFEO contribute to the LIF spectrum. A comparison between the experimental and calculated spectra confirms the expected long-range field effects of the CH F group on electronic transition energies and bond strengths, especially in the excited electronic (B̃) state. Although TFEO has only one conformer, its LIF spectrum is highly congested, which is attributed to the interaction between CO stretch and the -CF internal rotation.