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

Abstract

Phosphorus (III) oxyhalide OP–X molecules (X=F, Cl) are produced by an on-line process of POCl 3 passed over heated silver. The obtained OPCl reacts with sodium fluoride NaF to produce OPF. 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 OPF 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 Møller–Plesset second-order perturbation theory (MP2) calculations were performed to determine the geometry, total energy and vibrational frequency of OPF and OPCl.