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

We focus upon two properties, the electrostatic potential V ( r ) and the average local ionization energy {article}{empty}{document}Ī(r){document} . When evaluated on molecular surfaces, V S ( r ) and {article}{empty}{document}ĪS(r){document} can be useful tools for analyzing and predicting reactive behavior. V S ( r ) is most reliable with respect to noncovalent interactions; when electrophilic attack and some degree of charge transfer are involved, then the combination of V S ( r ) and {article}{empty}{document}ĪS(r){document} can be quite effective. They play complementary roles: V S ( r ) reveals the regions of the molecule to which an electrophile would initially be attracted, and {article}{empty}{document}ĪS(r){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.