Electron density analysis of substituent effects in substituted benzenes

Abstract

Electron projection functions and the corresponding difference functions relative to benzene are computed for π and σ electronic systems of several substituted benzenes, fluorobenzene, toluene and anilinium cation, and idealized model substituents, benzene with an external point positive charge and benzene with an external dipole. The results are plotted and integrated difference populations are compared with Mulliken populations. The later give good agreement, especially for π-systems, but obscure the underlying polarization especially evident in σ systems.