Atom and Bond Fukui Functions and Matrices: A Hirshfeld-I Atoms-in-Molecule Approach

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• 作者：Dr. Ofelia B. O&ntilde ; a ; Olivier De Clercq ; Dr. Diego R. Alcoba ; Prof. Dr. Alicia Torre ; Prof. Dr. Luis Lain ; Prof. Dr. Dimitri Van Neck and Prof. Dr. Patrick Bultinck
• 刊名：ChemPhysChem
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：17
• 期：18
• 页码：2881-2889
• 全文大小：834K
• ISSN：1439-7641

文摘

The Fukui function is often used in its atom-condensed form by isolating it from the molecular Fukui function using a chosen weight function for the atom in the molecule. Recently, Fukui functions and matrices for both atoms and bonds separately were introduced for semiempirical and ab initio levels of theory using Hückel and Mulliken atoms-in-molecule models. In this work, a double partitioning method of the Fukui matrix is proposed within the Hirshfeld-I atoms-in-molecule framework. Diagonalizing the resulting atomic and bond matrices gives eigenvalues and eigenvectors (Fukui orbitals) describing the reactivity of atoms and bonds. The Fukui function is the diagonal element of the Fukui matrix and may be resolved in atom and bond contributions. The extra information contained in the atom and bond resolution of the Fukui matrices and functions is highlighted. The effect of the choice of weight function arising from the Hirshfeld-I approach to obtain atom- and bond-condensed Fukui functions is studied. A comparison of the results with those generated by using the Mulliken atoms-in-molecule approach shows low correlation between the two partitioning schemes.