A group electronegativity equalization scheme including external potential effects.
By calculating the electron affinity and ionization energy of different functional groups, CCSD electronegativity values are obtained, which implicitly account for the effect of the molecular environment. This latter is approximated using a chemically justified point charge model. On the basis of Sanderson's electronegativity equalization 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 electronegativity equalization 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 functional groups, without having to rely on cumbersome calibrations. A very satisfactory correlation is obtained between these charge transfers and those obtained from an ab initio calculation of the entire molecule.
Leyssens
Tom
T
Laboratoire de Chimie Quantique, Bâtiment Lavoisier, Université Catholique de Louvain (UCL), place Louis Pasteur 1, B-1348 Louvain-la-Neuve, Belgium. t.leyssens@chim.ucl.ac.be
Geerlings
Paul
P
Peeters
Daniel
D