Thirty years of continuum solvation chemistry: a review, and prospects for the near future

Abstract.

With the recent occurrence of the 30^th anniversary of the first quantum mechanical continuum solvent code (Rinaldi D, Rivail J-L (1973) Theor Chim Acta 32:57), it seems like an appropriate moment to briefly review the variety of continuum QM models now available. This paper begins with such an overview, before shifting the discussion to a critical examination of some aspects of the basic theory, taking as the definition and evaluation of the solvation energy as an example. Advantages and disadvantages of using continuum-discrete models are examined, with particular attention paid to the evaluation of the solute’s response properties. Some guidelines, and an operative definition of specific solute-solvent interactions, are presented. Then the paper moves on to examine problems regarding solutes of very large size, as well as complex systems. An example of the latter is the surface enhancing properties of large metal cluster aggregates with respect to the optical properties of a chromophore in a liquid medium. The paper ends with some extrapolations to the near future, mostly based on the material presented in the preceding sections.