Electronegativity: The density functional viewpoint

Journal of Chemical Physics - Tập 68 Số 8 - Trang 3801-3807 - 1978
Robert G. Parr1, Robert A. Donnelly1, Mel Levy1, William E. Palke1
1Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27514

Tóm tắt

Precision is given to the concept of electronegativity. It is the negative of the chemical potential (the Lagrange multiplier for the normalization constraint) in the Hohenberg–Kohn density functional theory of the ground state: χ=−μ=−(∂E/∂N)v. Electronegativity is constant throughout an atom or molecule, and constant from orbital to orbital within an atom or molecule. Definitions are given of the concepts of an atom in a molecule and of a valence state of an atom in a molecule, and it is shown how valence-state electronegativity differences drive charge transfers on molecule formation. An equation of Gibbs–Duhem type is given for the change of electronegativity from one situation to another, and some discussion is given of certain relations among energy components discovered by Fraga.

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