ON STATIC JAHN-TELLER DISTORTION OF GROUND STATE OF VANADIUM TETRACHLORIDE

A simple treatment of the static Jahn-Teller effect in the ground state of VCl4 is made along the lines of the force formulation of Clinton and Rice. Assuming that the doubly-degenerate e-type orbital responsible for the deformation is simply a 3d atomic orbital on the vanadium atom, it has been shown, using Watson's SCF atomic orbitals, that the static distortion from an idealized tetrahedral shape is so small as not to be detectable. These results are not qualitatively inconsistent with recent theoretical and experimental investigations. Uncertainties in our knowledge of the fundamental vibration frequencies prevent more definite predictions. The use of Slater 3d atomic orbitals for vanadium leads to an unrealistically large increase in the tetrahedral deformation and distortion energy. But replacement of the purely atomic 3d orbital by a delocalized molecular orbital for the e electron leads to only a very small change (about 1 per cent) in the bond length difference between VCl4+ and VCl4. © 1969, Taylor & Francis Group, LLC. All rights reserved.