Frozen-Density Embedding Potentials and Chiroptical Properties.

Abstract

The efficacy of the frozen density embedding (FDE) approach to the simulation of solvent effects is examined for two key chiroptical properties-specific rotation and circular dichroism spectra. In particular, we have investigated the performance of a wave function-theory-in-density-functional-theory (WFT-in-DFT) FDE approach for computing such properties for the small, rigid chiral compound (P)-dimethylallene interacting with up to three water molecules. Although the solvent potential is obtained through DFT, the optical response is computed using coupled cluster linear response theory for mixed electric and magnetic field perturbations. We find that the FDE potential generally yields too small a shift from the isolated molecule as compared to that introduced by the explicit solvent. In one case, the FDE potential fails to reproduce a change in sign of the ORD in which the solute interacts with two solvent molecules. The source of these errors is due primarily to the lack of solvent response to the external field and is analyzed in terms of solvent-solute charge transfer excitations.