Ab initio study of the force constants of inorganic molecules ONF and NF3

The force constants of ONF and NF₃ have been determined from Hartree-Fock ab initio wavefunctions by the force method. Three different Gaussian basis sets, ranging from 7s3p augmented with functions on the bonds to 5s2p, were used for ONF. Only the smallest basis was applied to NF₃. The results show remarkable agreement with experiment, especially for the coupling constants. The NF stretching force constant is greatly overestimated in calculations with the 5s2p basis. The calculated force field makes it possible to exclude sets of force constants which are unphysical but compatible with the experimental data. The results show that even calculations with 5s2p basis sets can contribute to the determination of force fields.The experimental value of the $\text{ON}\text{β}$ coupling constant in ONF ranges between 0.27 and 0.54 mdyn; our calculations corroborate the higher value. An estimation of the calculated molecular geometries is given.