Pentacoordinated Molecules. VII. The Atomic Polarization and Dielectric Properties of PCl4F, PCl3F2, and PCl2F3 in Solution and in the Pure Liquid State

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Abstract
From measurements of the molecules PCl4F, PCl3F2 and PCl2F3 in cyclohexane solution, molar polarizations and refractions are calculated. The atomic polarizations for PCl3F2 (6.6 cc) and PCl2F3 (6.0 cc) approximate that found for PF5 (6.2 cc) and represent from 20%—40% of the induced polarization. The low‐frequency bending vibrations of these trigonal bipyramids are shown to be the principal source of the high atomic polarization values. A value of 4.5 cc is estimated for PCl4F. The temperature dependence of the dielectric constants and densities of the molecules in the pure liquid state also were measured. Application of the Onsager—Kirkwood theory gives dipole moments in good agreement with precise gas‐phase values. A similar comparison is made for the moments from the solution study for this series of low dipole halides.