The High-Resolution Mid-infrared FT Spectrum of Difluorodioxirane CF2O2: The Ground, ν1, ν2 and ν8 States

Abstract

The infrared spectrum of CF2O2 has been studied in the 800-1600 cm−1 region with a resolution of ca. 0.003 cm−1. Rotational fine structure was resolved, and the supposed cyclic difluorodioxirane structure with C2v symmetry, κ = −0.0632, was confirmed. The ν1 and ν2 bands, which reveal a-type structure and are centered at 1466.591 and 917.905 cm−1, respectively, and the c-type band ν8 centered at 1062.102 cm−1 have been analyzed employing Watson′s A-reduced Hamiltonian in the Ir representation. For each of these bands, between 4100 and 5600 lines were fitted, with σ = 3.5-4 × 10−4 cm−1. No perturbations were found. Ground state constants of the novel CF2O2 molecule were determined for the first time from a fit of ca. 7500 ground state combination differences formed from transitions belonging to ν1, ν2, and ν8, which were fitted with σ = 4 × 10−4 cm−1. The rotational constants A0 = 0.26575541(28) cm−1, B0 = 0.21095653(14) cm−1, and C0 = 0.16266791(15) cm−1 were determined. Assuming a CF bond length of 131.5 pm, the structural parameters d(CO) = 134.9 pm, d(OO) = 157.6 pm, and ∠ (FCF) 109.05° were derived.