Equilibrium structure and internal rotation in B2F4 from electron diffraction and spectroscopic data and quantum chemical calculations

Electron diffraction (ED) data for B2F4 recorded by Hedberg et al. over the temperature range -80 to +150degreesC have been used to obtain equilibrium geometry of this molecule in the framework of a large-amplitude motion model. The torsional coordinate has been adiabatically separated from the rest of vibrations. Two types of constraints applied to obtain ab initio torsional potential energy function (PEF) and the parameters of the geometry relaxation are discussed. The relations between anharmonic interaction force constants and the parameters of the geometry relaxation are briefly considered. Ab initio force constant matrices for rigid vibrational coordinates as well as large-amplitude torsional PEF have been scaled in the procedure of simultaneous fitting to the ED data and experimental vibrational frequencies. The resulting equilibrium geometry and potential function provided good fit to both ED and spectroscopic data. As expected, the results for the equilibrium geometry obtained from separate ED patterns recorded at different temperatures did not show noticeable temperature trend. The determined equilibrium structural parameters for B2F4 are: r(e)(B-B) = 1.719(4) Angstrom, r(e)(B-F) = 1.309(2) Angstrom, angleBBF = 121.1(1)degrees. Uncertainties given in parentheses include three times standard deviation and a systematic error. The rotational barrier height was evaluated as 160(50) cm(-1).