It is important to re-emphasize that the electrostatic component of the solvation free energy is not a physical observable. Thus, it is impossible to assert on any basis other [Pg.405]

C. Curutchet, C. J. Cramer, D. G. Truhlar, D. Rinaldi, M. F. Ruiz-Lopez, M. Orozco and F. J. Luque, Electrostatic component of solvation comparison of SCRF continuum models, J. Comput. Chem., 24 (2003) 284—297. [Pg.335]

In describing the results from SCRF calculations, it is useful to keep careful track of the various components of die energy. The electrostatic component of the solvation free energy is the difference between the energy in the gas phase and the energy in solution. This may be written [Pg.397]

The solution of these differential equations yields the total electrostatic potential at any point r. Assuming a linear response approximation the electrostatic component of solvation can be obtained as of the work necessary to generate the solvent reaction potential, which can be determined by simply computing the ratio of potential generated by the solute in vacuo to the total potential around the solute (Equation (4.34)). [Pg.515]

CM1 charges in the calculation of AGenp, corrections for charge inadequacies appear in G " )s and it is not possible to separate the electrostatic and non-electrostatic components of the free energy of solvation. [Pg.52]

The present chapter thus provides an overview of the current status of continuum models of solvation. We review available continuum models and computational techniques implementing such models for both electrostatic and non-electrostatic components of the free energy of solvation. We then consider a number of case studies, with particular focus on the prediction of heterocyclic tautomeric equilibria. In the discussion of the latter we center attention on the subtleties of actual chemical systems and some of the dangers of applying continuum models uncritically. We hope the reader will emerge with a balanced appreciation of the power and limitations of these methods. [Pg.4]

Support to these assumptions has recently come from the analysis of the coupling between electrostatic and dispersion-repulsion contributions to the solvation of a series of neutral solutes in different solvents [31]. It has been found that the explicit inclusion of both electrostatic and dispersion-repulsion forces have little effect on both the electrostatic component of the solvation free energy and the induced dipole moment, as can be noted from inspection of the data reported in Table 3.1. These results therefore support the separate calculation of electrostatic and dispersion-repulsion components of the solvation free energy, as generally adopted in QM-SCRF continuum models. [Pg.324]

Abstract This chapter reviews the theoretical background for continuum models of solvation, recent advances in their implementation, and illustrative examples of their use. Continuum models are the most efficient way to include condensed-phase effects into quantum mechanical calculations, and this is typically accomplished by the using self-consistent reaction field (SCRF) approach for the electrostatic component. This approach does not automatically include the non-electrostatic component of solvation, and we review various approaches for including that aspect. The performance of various models is compared for a number of applications, with emphasis on heterocyclic tautomeric equilibria because they have been the subject of the widest variety of studies. For nonequilibrium applications, e.g., dynamics and spectroscopy, one must consider the various time scales of the solvation process and the dynamical process under consideration, and the final section of the review discusses these issues. [Pg.1]

Most of the models described above have also been implemented at correlated levels of tlieory, including perturbation theory. Cl, and coupled-cluster theory (of course, the DFT SCRF process is correlated by construction of the functional). Unsurprisingly, if a molecule is subject to large correlation effects, so too is the electrostatic component of its solvation free energy. [Pg.401]

See also in sourсe #XX -- [ Pg.262 , Pg.263 , Pg.264 , Pg.265 , Pg.266 , Pg.267 , Pg.268 , Pg.269 ]

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