Continuum embedding models are widely used to incorporate solvent effects in quantum chemistry. The necessity to explicitly simulate solvent molecules is lifted by modelling the medium as a structureless dielectric continuum. A plethora of different realizations of this basic idea have been developed over time. The various electrostatic models are, despite their formal differences, all similar in the underlying physical model. The treatment of non-electrostatic solute-solvent interactions on the other hand is far less unambiguous, and various fundamentally different schemes exist. It has recently been shown that the Self-Consistent Continuum Solvation (SCCS) model can be reduced from a four parameter to an effective single parameter model without significantly losing accuracy. [1] Experimental data used in the parameterization is gathered in the Solv@TUM database [2]. This database, in contrast to other solvation databases, puts particular emphasis on non-aequeous solvents. We investigate here whether the observations from ref. [1] can be transferred to other implicit solvation models, in particular the multipole expansion (MPE) model. Finally, we also explore the possibility of other, equally simplistic post-SCF schemes based on solute specific descriptors. Moreover, the descriptor which results in the best fit gives us valuable insight about which phenomena beyond electrostatic interactions dominate solvation in the respective solvents.

Modelling nonelectrostatic solute-solvent interactions in continuum embedding

2019 Fall National Meeting

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