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Towards an Accurate Model for Halogens in Aqueous Solutions

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Quantum Modeling of Complex Molecular Systems

Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 21))

Abstract

The overwhelming progress and constant evolution of computational and theoretical methods in chemistry have provided us a more detailed molecular description of some complex molecular properties. Our group has intended to do so for an old problem: the solvatochromic properties of halogens in aqueous systems. There are beautiful experiments that show how sensitive Br2 and Cl2 are to the structure of the environment around them. In this chapter, we present the tests and calculations performed with different theoretical methods to identify their reliability as pieces of a multi-scale study aimed to address open questions related with this phenomenon. We used different approaches to explicitly take into account the solvent effect and tested several theoretical methods on the solvatochromic effect of small clusters. The combination of a semiempirical Born-Oppenheimer molecular dynamics study (SEBOMD) of Br2 in liquid water solution using PM3-PIF and then, the evaluation of the effect the closest water molecules have on the shifts are presented. This is a first step towards a robust multi-scale protocol ad hoc designed for these systems.

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Notes

  1. 1.

    sigma-hole: A region of electropositive potential due to the depletion of electron density occurring at the ends of the covalent sigma X-Y bond. It can favorably interact with a lone pair of electrons on a heteroatom from the donor.

  2. 2.

    Nomenclature 5n6m indicates a water cage composed of n pentagonal and m hexagonal faces.

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Acknowledgments

Several colleagues have enriched the insight gained up to now in this subject; we would like to thank A. Apkarian, N. Halberstadt, K. C. Janda, O. Roncero and M. F. Ruiz-López for many valuable comments and discussions. This work has been funded by CONACYT 79975 and 128065. AAT and FABR gratefully acknowledges scholarships from CONACYT.

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Authors and Affiliations

  1. Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, 62209, Cuernavaca, Mexico

    M. I. Bernal-Uruchurtu, A. Alcaraz Torres, F. A. Batista Romero & R. Hernández-Lamoneda

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  1. M. I. Bernal-Uruchurtu
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  2. A. Alcaraz Torres
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  3. F. A. Batista Romero
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  4. R. Hernández-Lamoneda
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Correspondence to M. I. Bernal-Uruchurtu .

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Editors and Affiliations

  1. UMR 7565—SRSMC, Université de Lorraine, Nancy-Vandoeuvre, France

    Jean-Louis Rivail

  2. UMR 7565—SRSMC, Université de Lorraine, Nancy-Vandoeuvre, France

    Manuel Ruiz-Lopez

  3. UMR 7565—SRSMC, Université de Lorraine, Nancy-Vandoeuvre, France

    Xavier Assfeld

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Bernal-Uruchurtu, M.I., Alcaraz Torres, A., Batista Romero, F.A., Hernández-Lamoneda, R. (2015). Towards an Accurate Model for Halogens in Aqueous Solutions. In: Rivail, JL., Ruiz-Lopez, M., Assfeld, X. (eds) Quantum Modeling of Complex Molecular Systems. Challenges and Advances in Computational Chemistry and Physics, vol 21. Springer, Cham. https://doi.org/10.1007/978-3-319-21626-3_9

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