The complementary roles of molecular surface electrostatic potentials and average local ionization energies with respect to electrophilic processes

Abstract

AbstractWe focus upon two properties, the electrostatic potential V(r) and the average local ionization energy \documentclass{article}\pagestyle{empty}\begin{document}$\bar{I}(\mathbf{r})$\end{document}. When evaluated on molecular surfaces, VS(r) and \documentclass{article}\pagestyle{empty}\begin{document}$\bar{I}_{S}(\mathbf{r})$\end{document} can be useful tools for analyzing and predicting reactive behavior. VS(r) is most reliable with respect to noncovalent interactions; when electrophilic attack and some degree of charge transfer are involved, then the combination of VS(r) and \documentclass{article}\pagestyle{empty}\begin{document}$\bar{I}_{S}(\mathbf{r})$\end{document} can be quite effective. They play complementary roles: VS(r) reveals the regions of the molecule to which an electrophile would initially be attracted, and \documentclass{article}\pagestyle{empty}\begin{document}$\bar{I}_{S}(\mathbf{r})$\end{document} indicates the ease of charge transfer at these and other sites. Four examples of such complementarity are discussed, involving benzene derivatives, guanine and cytosine, furan and pyrrole, and binary hydrides. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem, 2002