Atomic charges in ozone, carbon monoxide, silylene, silaketene and dimethylsilaketene (for both the pyramidal minimum and the planar transition state), 2-methyl-2-silacyclopropanone, ethylenebromonium cation (open and bridged), (Z)-1,3-butadiene, 1,3-cyclopentadiene, cyclopropene, methylenecyclopropene, the transition state for the Diels-Alder reaction between 1,3-cyclopentadiene and cyclopropene, and (E,E,E,E,E)-1,3,5,7,9-decapentaene have been calculated within the recently introduced GAPT population analysis. Effects of different basis sets and electron correlation on the atomic charges have been examined. On the basis of these studies it is found that the GAPT population analysis should be recommended as a standard tool for analyzing the electronic structure of organic molecules and transition states. © 1990, American Chemical Society. All rights reserved.