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Open Access Understanding Non-Covalent Interactions: Correlated Energy Decomposition Analysis and Applications to Halogen Bonding

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Non-covalent interactions play a primordial role in chemistry. Beyond their quantification, the detailed understanding of their physical processes is necessary to rationalize chemical trends and improve designs of chemical systems. Energy decomposition analyses allow detailed insight into non-covalent interactions by extracting electrostatics, Pauli repulsion, polarization, dispersion and charge transfer components from interaction energies. Recent work has demonstrated that electronic correlation influenced significantly all of these energy components, whereas previous decompositions only partitioned correlation between dispersion and charge transfer. The MP2 energy decomposition analysis with Absolutely Localized Molecular Orbitals (MP2 ALMO-EDA) takes these results fully into account and offers a correlation correction for each extracted component. A recent detailed investigation of the CCSD dispersion energy showed that a small number of virtual orbitals is sufficient to describe dispersion interactions accurately in the long-range, which potentially offers a basis-set independent definition of dispersion. Finally, we present an application of MP2 ALMO-EDA to a series of unusual halogen bonding complexes where charge transfer dominates over the electrostatic σ-hole interaction.

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Document Type: Research Article

Affiliations: 1: Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California Berkeley, California, 94720 USA; Chemical Sciences Division, Lawrence Berkeley National Laboratory Berkeley, California, 94720 USA. [email protected] 2: Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, IL 60439 USA 3: Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California Berkeley, California, 94720 USA; Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley, California, 94720 USA

Publication date: April 1, 2018

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  • International Journal for Chemistry and Official Membership Journal of the Swiss Chemical Society (SCS) and its Divisions

    CHIMIA, a scientific journal for chemistry in the broadest sense, is published 10 times a year and covers the interests of a wide and diverse readership. Contributions from all fields of chemistry and related areas are considered for publication in the form of Review Articles and Notes. A characteristic feature of CHIMIA are the thematic issues, each devoted to an area of great current significance.

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