How to Model Solvent Effects on Molecular Properties Using Quantum Chemistry? Insights from Polarizable Discrete or Continuum Solvation Models

We present a comparative study of solvent effects on the 15N NMR shielding constants and the lowest electronic excitation energy (n --> pi*) in the three diazines (pyrazine, pyrimidine, and pyridazine) in aqueous solution. This solvent is modeled using either a polarizable continuum model (PCM) or a discrete polarizable model (DPM). We analyze the results obtained with the two models in terms of differences/similarities in the reaction field produced at the solute. The PCM reaction field is found to be quite sensitive to the dimension of the cavity and so are the molecular properties. However, constructing the cavity so that the DPM and PCM reaction fields become similar in magnitude leads to quite similar results for the studied molecular properties modeling the solvent using either the PCM or the DPM. Compared to experimental data, the most accurate predicted results are obtained by describing the closest water molecules at the same level of sophistication as that of the solute, whereas the bulk solvent may be described using either PCM or MM. Finally, a comparison with geometry-optimized clusters seems to show that it is important to check potential deficiencies in the force field in order for this to treat hydrogen bonding in a consistent manner.