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Atom and bond Fukui functions and matrices : a Hirshfeld-I atoms-in-molecule approach

(2016) CHEMPHYSCHEM. 17(18). p.2881-2889
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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 Huckel 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.
Keywords
atoms in molecules, frontier molecular orbitals, Fukui functions, DUAL-DESCRIPTOR MATRICES, DEGENERATE GROUND-STATES, FRONTIER-ELECTRON THEORY, CHEMICAL-REACTIVITY, ELECTRONEGATIVITY EQUALIZATION, FUNCTION INDEXES, ORBITAL THEORY, NON-NEGATIVITY, PAIR DENSITY, FRAMEWORK

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Chicago
Oña, Ofelia B, Olivier De Clercq, Diego R Alcoba, Alicia Torre, Luis Lain, Dimitri Van Neck, and Patrick Bultinck. 2016. “Atom and Bond Fukui Functions and Matrices : a Hirshfeld-I Atoms-in-molecule Approach.” Chemphyschem 17 (18): 2881–2889.
APA
Oña, O. B., De Clercq, O., Alcoba, D. R., Torre, A., Lain, L., Van Neck, D., & Bultinck, P. (2016). Atom and bond Fukui functions and matrices : a Hirshfeld-I atoms-in-molecule approach. CHEMPHYSCHEM, 17(18), 2881–2889.
Vancouver
1.
Oña OB, De Clercq O, Alcoba DR, Torre A, Lain L, Van Neck D, et al. Atom and bond Fukui functions and matrices : a Hirshfeld-I atoms-in-molecule approach. CHEMPHYSCHEM. 2016;17(18):2881–9.
MLA
Oña, Ofelia B, Olivier De Clercq, Diego R Alcoba, et al. “Atom and Bond Fukui Functions and Matrices : a Hirshfeld-I Atoms-in-molecule Approach.” CHEMPHYSCHEM 17.18 (2016): 2881–2889. Print.
@article{8501645,
  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 Huckel 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.},
  author       = {O{\~n}a, Ofelia B and De Clercq, Olivier and Alcoba, Diego R and Torre, Alicia and Lain, Luis and Van Neck, Dimitri and Bultinck, Patrick},
  issn         = {1439-4235},
  journal      = {CHEMPHYSCHEM},
  keyword      = {atoms in molecules,frontier molecular orbitals,Fukui functions,DUAL-DESCRIPTOR MATRICES,DEGENERATE GROUND-STATES,FRONTIER-ELECTRON THEORY,CHEMICAL-REACTIVITY,ELECTRONEGATIVITY EQUALIZATION,FUNCTION INDEXES,ORBITAL THEORY,NON-NEGATIVITY,PAIR DENSITY,FRAMEWORK},
  language     = {eng},
  number       = {18},
  pages        = {2881--2889},
  title        = {Atom and bond Fukui functions and matrices : a Hirshfeld-I atoms-in-molecule approach},
  url          = {http://dx.doi.org/10.1002/cphc.201600433},
  volume       = {17},
  year         = {2016},
}

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