| Abstract
| - By calculating the electron affinity and ionization energy of different functional groups, CCSD electronegativityvalues are obtained, which implicitly account for the effect of the molecular environment. This latter isapproximated using a chemically justified point charge model. On the basis of Sanderson's electronegativityequalization principle, this approach is shown to lead to reliable “group in molecule” electronegativities.Using a slight adjustment of the modeled environment and first-order principles, an electronegativityequalization scheme is obtained, which implicitly accounts for the major part of the external potential effect.This scheme can be applied in a predictive manner to estimate the charge transfer between two functionalgroups, without having to rely on cumbersome calibrations. A very satisfactory correlation is obtained betweenthese charge transfers and those obtained from an ab initio calculation of the entire molecule.
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