Refractive indices for molecular crystals are obtained from Hartree-Fock wavefunctions constrained to reproduce a set of experimental X-ray structure factors. Coupled-perturbed Hartree-Fock theory is used to calculate the in-crystal effective polarizabilities from which the refractive indices are obtained, thus eliminating the need for the calibration procedure used in earlier work by Whitten et al. [J. Chem. Phys. 2006, 125, 174505]. The results clearly demonstrate that these X-ray constrained Hartree-Fock (XCHF) wavefunctions reflect genuine effects of intermolecular interactions in crystals. Molecular dipole moments are consistently in excellent agreement with ab initio MP2 estimates that incorporate the effects of the crystal field. Consistent agreement of the XCHF refractive indices with experimental measurements at optical frequencies confirms that this approach can provide both meaningful results and considerable insight into the relative importance of molecular properties and crystal field effects in determining the detailed nature of the refractivity tensor. © 2009 the Owner Societies.