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Hydrogen-bonded contact ion pair in gaseous chloroethane: a multi-reference configuration interaction with singles and doubles (MR-CISD) study including extensivity corrections

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Abstract

Details concerning the energetics and structure of the ion pair in gaseous chloroethane, obtained at the multi-reference configuration interaction with singles and doubles (MR-CISD) level, are given. It is formed in the third excited state (31A′), and it can be classified as a hydrogen-bonded contact ion pair, although from its total binding energy of 3.28 eV (including extensivity corrections, at the MR-CISD + Q level with the aug-cc-pVTZ basis set, and including zero-point energy corrections) only 0.14 eV is due to an underlying hydrogen bond. It is a highly polar structure, with a dipole moment of 9.56 D. As compared to previous systems for which the same type of bond has been observed, it has a much lower hydrogen-bond energy and a much larger distance between the charge centers. The three lowest frequency vibrational modes of the HBCIP correspond to intermolecular cation–anion modes. The structure here obtained brings important structural questions for HCFCs derived from chloroethane.

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Acknowledgments

The authors thank the following Brazilian agencies: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Project 303884/2018-5 and 423112/2018-0), Coordenacão de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Financiadora de Estudos e Projetos (FINEP). They are also grateful to the CESUP/UFRGS for the computational facilities and to Prof. Fernando Ornellas from whom many important Quantum Chemistry lessons have been learned.

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  1. Universidade Federal da Paraíba, João Pessoa, PB, 58051–900, Brazil

    Elizete Ventura & Silmar Andrade do Monte

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Ventura, E., do Monte, S.A. Hydrogen-bonded contact ion pair in gaseous chloroethane: a multi-reference configuration interaction with singles and doubles (MR-CISD) study including extensivity corrections. Theor Chem Acc 139, 49 (2020). https://doi.org/10.1007/s00214-020-2561-8

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