Gas-phase infrared spectra of phosphorus (III) oxyhalide: Experimental and theoretical study of OPF and OPCl

Phosphorus (III) oxyhalide O = P - X molecules (X = F, Cl) are produced by an on-line process of POCl3 passed over heated silver. The obtained OPCl reacts with sodium fluoride NaF to produce OFF. The low resolution gas-phase Fourier transform infrared spectra, reported for the first time, show four strong bands centered at 1357.2, 1272.8, 821.5 and 491.6 cm(-1). The first two bands refer to the O = P stretching of OFF and OPCl, respectively. The other two are referring to the P-X stretching mode for X = F and Cl, respectively. Ab initio self-consistent-field (SCF) molecular orbital (MO) and Moller-Plesset second-order perturbation theory (MP2) calculations were performed to determine the geometry, total energy and vibrational frequency of OFF and OPCl. (C) 1998 Elsevier Science B.V.