How accurately various model intermolecular interaction functions are able to reproduce the detailed structure of orthorhombic TeF6 has been investigated by molecular packing analyses. Experimental structure parameters were extrapolated to the vibrationless limit. Model potential functions were six- and seven-site pairwise additive atom-atom functions including partial charges. Lennard-Jones and Buckingham functions worked equally well. Scoles combining rules gave more consistent results than the conventional Lorenz-Berthelot and Good-Hope rules, Partial charges of approximately 0.21 e(-) on fluorine atoms gave the most accurate account of the experimental structure parameters. Potential functions based solely on interactions between fluorine sites were distinctly inferior to functions explicitly incorporating tellurium atoms, Although not required to do so by physical principles, the optimal partial charges for intermolecular interactions agreed well with charges derived for individual molecules by the Rappe-Goddard charge equilibration method.