The merits of the frozen-density embedding scheme to model solvatochromic shifts

Abstract

We investigate the usefulness of a frozen-density embedding scheme within density-functional theory [J. Phys. Chem. 97, 8050 (1993)] for the calculation of solvatochromic shifts. The frozen-density calculations, particularly of excitation energies have two clear advantages over the standard supermolecule calculations: (i) calculations for much larger systems are feasible, since the time-consuming time-dependent density functional theory (TDDFT) part is carried out in a limited molecular orbital space, while the effect of the surroundings is still included at a quantum mechanical level. This allows a large number of solvent molecules to be included and thus affords both specific and nonspecific solvent effects to be modeled. (ii) Only excitations of the system of interest, i.e., the selected embedded system, are calculated. This allows an easy analysis and interpretation of the results. In TDDFT calculations, it avoids unphysical results introduced by spurious mixings with the artificially too low charge-transfer excitations which are an artifact of the adiabatic local-density approximation or generalized gradient approximation exchange-correlation kernels currently used. The performance of the frozen-density embedding method is tested for the well-studied solvatochromic properties of the n-->pi(*) excitation of acetone. Further enhancement of the efficiency is studied by constructing approximate solvent densities, e.g., from a superposition of densities of individual solvent molecules. This is demonstrated for systems with up to 802 atoms. To obtain a realistic modeling of the absorption spectra of solvated molecules, including the effect of the solvent motions, we combine the embedding scheme with classical molecular dynamics (MD) and Car-Parrinello MD simulations to obtain snapshots of the solute and its solvent environment, for which then excitation energies are calculated. The frozen-density embedding yields estimated solvent shifts in the range of 0.20-0.26 eV, in good agreement with experimental values of between 0.19 and 0.21 eV.