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Issue 45, 2011
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Homolytic molecular dissociation in natural orbital functional theory

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Abstract

The dissociation of diatomic molecules of the 14-electron isoelectronic series N2, O2+2, CO, CN and NO+ is examined using the Piris natural orbital functional. It is found that the method describes correctly the dissociation limit yielding an integer number of electrons on the dissociated atoms, in contrast to the fractional charges obtained when using the variational two-particle reduced density matrix method under the D, Q and G positivity necessary N-representability conditions. The chemistry of the considered systems is discussed in terms of their dipole moments, natural orbital occupations and bond orders as well as atomic Mulliken populations at the dissociation limit. The values obtained agree well with accurate multiconfigurational wave function based CASSCF results and the available experimental data.

Graphical abstract: Homolytic molecular dissociation in natural orbital functional theory

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Publication details

The article was received on 25 May 2011, accepted on 02 Aug 2011 and first published on 09 Sep 2011


Article type: Paper
DOI: 10.1039/C1CP21696A
Citation: Phys. Chem. Chem. Phys., 2011,13, 20129-20135
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    Homolytic molecular dissociation in natural orbital functional theory

    J. M. Matxain, M. Piris, F. Ruipérez, X. Lopez and J. M. Ugalde, Phys. Chem. Chem. Phys., 2011, 13, 20129
    DOI: 10.1039/C1CP21696A

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