Density functional theory solvent effects

Adamovic, I., Gordon, M. S. (2005). Solvent Effects on the Sn2 Reaction Application of the Density Functional Theory-Based Effective Fragment Potential Method,/ Phys. Chem. A, 109,1629-1636. 

Adamo, C., and F. Lelj. 1994. Equilibrium solvent effects in the framework of density functional theory. Application to the study of the thermodynamics of some organic and inorganic tautomereic equilibria. Chem. Phys. Lett. 223, 54. 

Riuz-Lopez, M. F., F. Bohr, M. T. C. Marlins-Costa, and D. Rinaldi. 1994. Studies of solvent effects using density functional theory. Co-operative interactions in H3N. . HBr proton transfer. Chem. Phys. Lett. 221, 109. 

Truong, T. N. and E. V. Stefanovich. 1995. A new method for incorporating solvent effects into classical, ab initio molecular-orbital and density functional theory frameworks for arbitrary shape cavity. Chem. Phys. Lett. 240, 253. 

THEORETICAL BASIS FOR THE TREATMENT OF SOLVENT EFFECTS IN THE CONTEXT OF DENSITY FUNCTIONAL THEORY... 

Theoretical considerations leading to a density functional theory (DFT) formulation of the reaction field (RF) approach to solvent effects are discussed. The first model is based upon isolelectronic processes that take place at the nucleus of the host system. The energy variations are derived from the nuclear transition state (ZTS) model. The solvation energy is expressed in terms of the electrostatic potential at the nucleus of a pseudo atom having a fractional nuclear charge. This procedure avoids the introduction of arbitrary ionic radii in the calculation of insertion energy, since all integrations involved are performed over [O.ooJ The quality of the approximations made are discussed within the frame of the Kohn-Sham formulation of density functional theory. 

Local density functional theory may be introduced within the RF model of solvent effects thorugh the induced electron density. The basic quantity for such a development is the linear density response function [39] ... 

In summary, density functional theory provides a natural framework to discuss solvent effects in the context of RF theory. A general expression giving the insertion energy of an atom or molecule into a polarizable medium was derived. This expression given in Eq (83), when treated within a first order perturbation theory approach (i.e. when the solute self-polarization... 

Another similar approach applies an explicit density-functional theory treatment to the solute molecules, while representing the contribution of the solvent molecules as an effective potential [105]. 

Model computational studies aimed at understanding structure-reactivity relationships and substituent effects on carbocation stability for aza-PAHs derivatives were performed by density functional theory (DFT). Comparisons were made with the biological activity data when available. Protonation of the epoxides and diol epoxides, and subsequent epoxide ring opening reactions were analyzed for several families of compounds. Bay-region carbocations were formed via the O-protonated epoxides in barrierless processes. Relative carbocation stabilities were determined in the gas phase and in water as solvent (by the PCM method). 

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