Evaluation of an Efficient 3D-RISM-SCF Implementation as a Tool for Computational Spectroscopy in Solution.

The 3D-RISM-SCF solvent-model implementation of Gusarov et al. [ J. Phys. Chem. A 2006, 110, 6083-6090] in the Amsterdam density functional program has been improved and extended. In particular, an accurate yet efficient representation of the solute electrostatic potential is provided. The Coulomb-potential fitting of many DFT codes can be used advantageously in this context. The extra effort compared to a point-charge representation is small for a given SCF cycle and compensated by faster SCF convergence. This allows applications to large solutes, as demonstrated by evaluation of the solvatochromism of Reichardt's dye. In general, TDDFT applications to excitation energies in solution stand out and are highlighted. Applications to the 17O NMR chemical shifts of N-methylformamide in different solvents also demonstrate the distinct advantages of 3D-RISM over continuum solvents. Limitations are observed in this case for water solvent, where the solvent shielding is overestimated. This shortcoming applies also to the 17O gas-to-liquid shift of water, where we used localized molecular orbital analyses for a deeper understanding. For such cases of extremely strong solute-solvent interactions, couplings between solute and solvent orbitals induced by the magnetic perturbation are relevant. These clearly require a quantum-mechanical treatment of the most closely bound solvent molecules. Except for such extreme cases, 3D-RISM-SCF is very well suited to treat solvent effects on NMR parameters. More serious limitations pertain to the treatment of vibrational spectra, where the absence of the coupling between solute and solvent vibrational modes limits the accuracy of applications of 3D-RISM-SCF. The reported extended, efficient, and numerically accurate 3D-RISM-SCF implementation should provide a useful tool to study chemical and spectroscopic properties of molecules of appreciable size in a realistic solvent environment.