The importance of the external potential on group electronegativity.
The electronegativity of groups placed in a molecular environment is obtained using CCSD calculations of the electron affinity and ionization energy. A point charge model is used as an approximation of the molecular environment. The electronegativity values obtained in the presence of a point charge model are compared to the isolated group property to estimate the importance of the external potential on the group's electronegativity. The validity of the "group in molecule" electronegativities is verified by comparing EEM (electronegativity equalization method) charge transfer values to the explicitly calculated natural population analysis (NPA) ones, as well as by comparing the variation in electronegativity between the isolated functional group and the functional group in the presence of a modeled environment with the variation based on a perturbation expansion of the chemical potential.
Leyssens
Tom
T
Laboratoire de Chimie Quantique, Bâtiment Lavoisier, Université catholique de Louvain, place Louis Pasteur 1, B-1348 Louvain-la-Neuve, Belgium. t.leyssens@chim.ucl.ac.be
Geerlings
Paul
P
Peeters
Daniel
D