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Issue 8, 2019
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A first step towards quantum energy potentials of electron pairs

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A first step towards the construction of a quantum force field for electron pairs in direct space is taken. Making use of topological tools (Interacting Quantum Atoms and the Electron Localisation Function), we have analysed the dependency of electron pairs electrostatic, kinetic and exchange–correlation energies upon bond stretching. Simple correlations were found, and can be explained with elementary models such as the homogeneous electron gas. The resulting energy model is applicable to various bonding regimes: from homopolar to highly polarized and even to non-conventional bonds. Overall, this is a fresh approach for developing real space-based force fields including an exchange–correlation term. It provides the relative weight of each of the contributions, showing that, in common Lewis structures, the exchange correlation contribution between electron pairs is negligible. However, our results reveal that classical approximations progressively fail for delocalised electrons, including lone pairs. This theoretical framework justifies the success of the classic Bond Charge Model (BCM) approach in solid state systems and sets the basis of its limits. Finally, this approach opens the door towards the development of quantitative rigorous energy models based on the ELF topology.

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The article was received on 07 Dec 2018, accepted on 25 Jan 2019 and first published on 29 Jan 2019

Article type: Paper
DOI: 10.1039/C8CP07509C
Citation: Phys. Chem. Chem. Phys., 2019,21, 4215-4223

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    A first step towards quantum energy potentials of electron pairs

    J. Munárriz, R. Laplaza, A. Martín Pendás and J. Contreras-García, Phys. Chem. Chem. Phys., 2019, 21, 4215
    DOI: 10.1039/C8CP07509C

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