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

Abstract

The widespread application of computational techniques to studies in biological, chemical and environmental sciences has led to a quest for important, characteristic molecular parameters that may be directly derived from these 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, understand and predict properties which depend upon solute–solvent interactions. The TLSER methodology was used to correlate and to attempt to understand and probe eight solvent scales commonly used in linear free energy relationships and physical organic chemistry. Correlations are presented which demonstrate the ability of the TLSER not only to predict values for these solvent scales, but which also serve as a probe to attempt to understand the underlying physical meaning of these solvent scales. This article is a US Government work and is in the public domain in the United States.