The structures and dipole moments of Ar-PF3 and Kr-PF3

The complexes of PF3 with Ar and Kr, were studied by Fourier transform microwave spectroscopy. The force constants and amplitudes of vibration for the van der Waals modes of the complexes and the average moments of inertia and structural parameters were estimated from the centrifugal distortion constants. The distance (Rc.m. )ave between the rare-gas atom and the center of mass of PF3 is 3.959 Å for the Ar complex and 4.077 Å for Kr while the angle (θc.m. )ave between the Rc.m. vector and the C3 axis of the PF3 is 69.30° and 67.25°, respectively. The dipole moments of both complexes and of free PF3 were determined. The induced dipole components estimated for the rare gas using electric fields from ab initio calculations of PF3 agree with the experimental values for a conformation with the rare gas over a PF2 face. The PF2 face conformation is also consistent with the observed and ab initio estimates of the 83 Kr nuclear quadrupole coupling constant for the 83 Kr–PF3 species.