Chapter 2

Dielectric continuum solvation

models and COSMO

2.1 THE BASIC IDEA AND ITS DEVELOPMENT

In 1920, Max Born, a Nobel Prize winner, .published some work

on the free energy of solvation of ions, AG~~ [21]. He conceived
the idea of approximating the solvent surrounding the ion as a
dielectric continuum. Defining a spherical boundary, between the
ion and the continuum by an effective ion-radius, R ran, he got the
simple result

AV~On t:S- 1 Q i~
eS 2Rio n (2.1)

Here, we introduce the convention of denoting the solvent by a

suffix, and the solute by a superscript index..Hence, es stands for
the dielectric constant of the solvent S, and Qmn is the total charge
of the ion. Surely, Born was aware that this is a crude
approximation, but his formula led to a qualitative understanding
of the experimentally observed values of solvation energies.
Indeed, it was later used to define ionic radii R i~ and thus it
became in some way a self-fulfilling prophecy.
Born's idea of the dielectric continuum solvation approxima-
tion became very popular, and many researchers worked on its
further development. Hence a brief overview of the most
important development steps will be given, but it is impossible
to mention all the different modifications and all workers who
have been contributing to this field. Readers who seek a broader
overview are referred to some reviews on continuum solvation
methods, e.g., by Cramer and Truhlar [22] or by Tomasi and
Persico [23]. The goal of the history given here is to enable

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