title: Atom and Bond Fukui Functions and Matrices: A Hirshfeld-I Atoms-in-Molecule Approach.
abstract: 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.
authors.affiliation: Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de la Plata, CCT La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas, Diag. 113 y 64 (s/n), Sucursal 4, CC 16, 1900, La Plata, Argentina.
authors.forename: Ofelia B
authors.initials: OB
authors.lastname: Oña
authors.affiliation: Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), 9000, Gent, Belgium.
authors.forename: Olivier
authors.initials: O
authors.lastname: De Clercq
authors.affiliation: Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires (Argentina), Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, 1428 Buenos, Aires, Argentina.
authors.forename: Diego R
authors.initials: DR
authors.lastname: Alcoba
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, E-48080, Bilbao, Spain.
authors.forename: Alicia
authors.identifier: http://orcid.org/0000-0002-5681-7074
authors.initials: A
authors.lastname: Torre
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, E-48080, Bilbao, Spain.
authors.forename: Luis
authors.identifier: http://orcid.org/0000-0002-7260-049X
authors.initials: L
authors.lastname: Lain
authors.affiliation: Center for Molecular Modeling, Ghent University, Technologiepark 903, B-9052, Zwijnaarde, Belgium.
authors.forename: Dimitri
authors.identifier: http://orcid.org/0000-0001-9687-1895
authors.initials: D
authors.lastname: Van Neck
authors.affiliation: Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), 9000, Gent, Belgium. Patrick.Bultinck@UGent.be.
authors.forename: Patrick
authors.identifier: http://orcid.org/0000-0003-2766-2672
authors.initials: P
authors.lastname: Bultinck
keywords: Fukui functions; atoms in molecules; frontier molecular orbitals