Local molecular properties and their use in predicting reactivity

Abstract

Expressions for the local electron affinity, electronegativity and hardness are derived in analogy to the local ionization energy introduced by Sjoberg, Murray and Politzer. The local polarizability is also defined based on an additive atomic orbital polarizability model that uses Rivail's variational technique. The characteristics of these local properties at molecular surfaces and their relevance to electrophilic aromatic substitution, to S_N2 reactivity and to the nucleophilicity of enolate ions are discussed. Figure The local ionization energy at the SES surfaces of methyl benzoate. The color scale ranges from 375 (blue) to 550 kcal mol⁻¹ (red). The blue areas are those for which interaction with an acceptor is most favorable.