Ground- and excited-state properties of solid argon under pressure

A self-consistent perturbation model for calculating the ground- and excited-state electronic properties of molecular and rare-gas crystals is presented. A tight-binding approximation is used, in which the effects of the crystal potential, calculated with local-density functionals, are included as a perturbation on the molecules (or atoms). The molecular (atomic) wave functions are then computed from standard Hartree-Fock theory. For the case of solid argon under pressure, a decrease in atomic volume causes a gain in free energy, which is partially balanced by the energy required to compress the atom. Calculated exciton energies for Ar disagree by only 2.5% with experimental values at zero pressure