Molecular basis of LFER. Modeling of the electronic substituent effect using fragment quantum self-similarity measures.
A new approach allowing the theoretical modeling of the electronic substituent effect is proposed. The approach is based on the use of fragment Quantum Self-Similarity Measures (MQS-SM) calculated from domain averaged Fermi Holes as new theoretical descriptors allowing for the replacement of Hammett sigma constants in QSAR models. To demonstrate the applicability of this new approach its formalism was applied to the description of the substituent effect on the dissociation of a broad series of meta and para substituted benzoic acids. The accuracy and the predicting power of this new approach was tested on the comparison with a recent exhaustive study by Sullivan et al. It has been shown that the accuracy and the predicting power of both procedures is comparable, but, in contrast to a five-parameter correlation equation necessary to describe the data in the study, our approach is more simple and, in fact, only a simple one-parameter correlation equation is required.
Gironés
Xavier
X
Institute of Computational Chemistry, University of Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain.
Carbó-Dorca
Ramon
R
Ponec
Robert
R