Linear Interaction Energy theory

Almlof M, Carlsson J, Aqvist J (2007) Improving the accuracy of the linear interaction energy method for solvation free energies. J Chem Theory Comput 3(6) 2162-2175... 

An approach that provides a general theoretical insight into the redox properties of a linearly combined multi-redox system has been presented by Aoki and Chen (75). The theory is constructed on the basis of interaction energies between neighboring redox sites, uqr,... 

These points indicate that the continuum theory expression of the free energy of activation, which is based on the Born solvation equation, has no relevance to the process of activation of ions in solution. The activation of ions in solution should involve the interaction energy with the solvent molecules, which depends on the structure of the ions, the solvent, and their orientation, and not on the Born charging energy in solvents of high dielectric constant (e.g., water). Consequently, the continuum theory of activation, which depends on the Born equation,fails to correlate (see Fig. 1) with experimental results. Inverse correlations were also found between the experimental values of the rate constant for an ET reaction in solvents having different dielectric constants with those computed from the continuum theory expression. Continuum theory also fails to explain the well-known Tafel linearity of current density at a metal electrode. ... 

The Kamlet-Taft u polarity/polarizability scale is based on a linear solvation energy relationship between the n it transition energy of the solute and the solvent polarity ( 1). The Onsager reaction field theory (11) is applicable to this type of relationship for nonpolar solvents, and successful correlations have previously been demonstrated using conventional liquid solvents ( 7 ). The Onsager theory attempts to describe the interactions between a polar solute molecule and the polarizable solvent in the cybotatic region. The theory predicts that the stabilization of the solute should be proportional to the polarizability of the solvent, which can be estimated from the index of refraction. Since carbon dioxide is a nonpolar fluid it would be expected that a linear relationship... 

A rational strategy in identifying structural parameters appropriate for QSRR analysis should start from the accepted theories of chromatographic separations. These structural parameters obtained. should quantify the abilities of analytes to take part in the postulated intermolecular interactions which determine chromatographic. separations. Empirical or semi-empirical structural parameters of analytes based on the solvatochromic comparison method and on the linear solvation energy relationships (LSER) belong to that categoiy of structural descriptors. 19,40). 

It is appropriate, perhaps, to mention here that imprudent application of linear combinations like equation 6.3 in basis set theory can lead to error. The interaction energy. j t, between two atoms A and B, separated by a... 

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