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A definition for the covalent and ionic bond index in a molecule

An approach based on Roby’s atomic projection operators

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Abstract

Formulae for hermitian operators representing covalent, ionic, and total bond indices are derived. The eigenstates of these operators come in pairs, and can be considered as bonding, anti-bonding and lone-pair orbitals. The form of these operators is derived by generalising the rule that the bond order be defined as the net number of bonding electron pairs. The percentage of covalency and ionicity of a chemical bond may be obtained, and bond indices can also be defined between groups of atoms. The calculation of the bond indices depends only on the electron density operator, and certain projection operators used to represent each atom in the molecule. Bond indices are presented for a series of first and second row hydrides and fluorides, hydrocarbons, a metal complex, a Diels–Alder reaction and a dissociative reaction. In general the agreement between the bond indices is in accord with chemical intuition. The bond indices are shown to be stable to basis set expansion.

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Authors and Affiliations

  1. Department of Mathematics, The University of Queensland, Brisbane, QLD, 4072, Australia

    Mark D. Gould

  2. Chemistry, Biomedical and Chemical Sciences, The University of Western Australia, 35 Stirling Hwy, Crawley, WA, 6009, Australia

    Christopher Taylor, Stephen K. Wolff, Graham S. Chandler & Dylan Jayatilaka

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  1. Mark D. Gould
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  2. Christopher Taylor
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  3. Stephen K. Wolff
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  4. Graham S. Chandler
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  5. Dylan Jayatilaka
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Gould, M.D., Taylor, C., Wolff, S.K. et al. A definition for the covalent and ionic bond index in a molecule. Theor Chem Account 119, 275–290 (2008). https://doi.org/10.1007/s00214-007-0282-x

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  • DOI: https://doi.org/10.1007/s00214-007-0282-x

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