High resolution infrared, microwave, and millimeter wave spectra of SeCF2 structure determination assisted by Ab initio calculations

Monoisotopic 80 Se=CF 2 has been prepared, and high resolution (2.5-3.3x10 -3 cm -1 ) Fourier transform infrared spectra in the v 3 (v 0 431.053 cm -1 ) and v 4 regions (v 0 1208.790 cm -1 ) have been recorded. The hitherto unknown rotational constants that were obtained by means of ground state combination differences assisted the search for microwave transitions of M SeCF 2 species, M=76, 77, 78, 80, and 82, in the 5-26 GHz range and of millimeter wave transitions for M=78 and 80 in the 152-240GHz region. Ground state constants up to quartic terms of the five isotopic species were determined by merging all available data. Excited state parameters of the v 3 = 1 and v 4 = 1 states were also determined. It is concluded that these states are unperturbed at the present level of accuracy, which is 4.5x10 -4 cm -1 for the rms deviation of more than 6000 (v 3 ) and 12000 IR transitions (v 4 ). Ab initio calculations at the correlated levels of second order Moller-Plesset pertubation theory using different basis sets were performed. Experimental and theoretical results were combined to deduce effective (r o ), average (r l ) and equilibrium (r e ) structural parameters. The equilibrium parameters are r(C-F) 1.309(2)A, r(C=Se) 1.739(2)A and Z(FCF) 107.74(4).

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