Jones and magnetoelectric birefringence of pure substances. A computational study

We present the first investigation of condensed-phase effects on the Jones (and magnetoelectric) birefringence of a set of nondipolar (CCl$_4$ and CS$_2$) and dipolar (nitro- and chloro-benzene) molecules using a recent implementation of the polarizable continuum model for cubic response functions at the time-dependent density-functional level of theory. The condensed-phase calculations have been performed on the neat liquids of the sample molecules using a nonequilibrium solvation scheme to properly account for the solute-solvent interactions in the presence of a frequency-dependent electromagnetic field. It is demonstrated that the condensed-phase effects as modelled by the polarizable continuum model can be substantial, increasing the observable birefringence by more than sixty percent in the case of carbon tetrachloride, and by a factor of more than three for carbon disulphide. Solvent effects are also substantial for the dipolar molecules, leading to an enhancement by a factor of roughly five for nitro-benzene and by a bit less than 30\% for chloro-benzene. Comparison is made with the results of experiment. Our calculated anisotropies confirm that the effect is below current experimental detection limits for CCl$_4$ and CS$_2$. We compute Jones constants of the same order of magnitude as the upper limits given in experiment for nitro- and chloro-benzene.