Using theoretical descriptors in linear free energy relationships: characterizing several polarity, acid and basicity scales

The widespread application of computational techniques to studies in biolog ical, chemical and environmental sciences has led to a quest for important, characteristic molecular parameters that may be directly derived from thes e computational methods. Theoretical linear solvation energy relationships (TLSER) combine computational molecular orbital parameters with the linear solvation energy relationship (LSER) of Kamlet and Taft to characterize, un derstand and predict properties which depend upon solute-solvent interactio ns. The TLSER methodology was used to correlate and to attempt to understan d and probe eight solvent scales commonly used in linear free energy relati onships and physical organic chemistry. Correlations are presented which de monstrate the ability of the TLSER not only to predict values for these sol vent scales, but which also serve as a probe to attempt to understand the u nderlying physical meaning of these solvent scales. This article is a US Go vernment work and is in the public domain in the United States.