Degenerate four-wave mixing in solution by cubic response theory and the polarizable continuum model.

We have derived and implemented the solvent contribution to the cubic response function for the polarizable continuum model in its integral equation formulation. The present formulation is valid both at the Hartree-Fock and at the Kohn-Sham density functional levels of theory, because both bear the same formal description of the solvent contribution through an additional additive term in the Hamiltonian operator. This new implementation is used to compute the solvent effect for the degenerate four-wave mixing process on three different classes of heteroaromatic chromophores: (I) triazine, benzoxazole, benzimidazole, and benzothiazole; (II) three benzothiazole derivatives; and (III) three tri-s-triazine derivatives. The results are first discussed in terms of the solvent effects on the calculated property and then compared to experimental data for the substrates of class (I) and (II).