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Journal of Molecular Modeling

, Volume 19, Issue 5, pp 2097–2106 | Cite as

Is the decrease of the total electron energy density a covalence indicator in hydrogen and halogen bonds?

  • Emilio L. Angelina
  • Darío J. R. Duarte
  • Nélida M. PeruchenaEmail author
Original Paper

Abstract

In this work, halogen bonding (XB) and hydrogen bonding (HB) complexes were studied with the aim of analyzing the variation of the total electronic energy density H(r b ) with the interaction strengthening. The calculations were performed at the MP2/6−311++G(2d,2p) level of approximation. To explain the nature of such interactions, the atoms in molecules theory (AIM) in conjunction with reduced variational space self-consistent field (RVS) energy decomposition analysis were carried out. Based on the local virial theorem, an equation to decompose the total electronic energy density H(r b ) in two energy densities, (−G(r b )) and 1/4∇2ρ(r b ), was derived. These energy densities were linked with the RVS interaction energy components. Through the connection between both decomposition schemes, it was possible to conclude that the decrease in H(r b ) with the interaction strengthening observed in the HB as well as the XB complexes, is mainly due to the increase in the attractive electrostatic part of the interaction energy and in lesser extent to the increase in its covalent character, as is commonly considered.

Keywords

AIM Energy decomposition Hydrogen/halogen bonds RVS Total electron energy density 

Notes

Acknowledgments

We acknowledge SECYT UNNE (Secretaría de Ciencia y Tecnología – Universidad Nacional del Nordeste), for financial support. E.L.A is a fellow researcher of CONICET (Consejo Nacional de Investigaciones Científicas y Técnicas), D.J.R.D. is a fellows of CONICET UNNE (Consejo Nacional de Investigaciones Científicas y Técnicas - Universidad Nacional del Nordeste) and N.M.P. is a career researcher of CONICET, Argentine. This work was supported by the Grants PICTO-UNNE (Proyecto de Investigación Científica y Tecnológica Orientado- Universidad Nacional del Nordeste) 089 and PIP CONICET (Proyecto de Investigación Plurianual – Consejo Nacional de Investigaciones Científicas y Técnicas) 095.

Supplementary material

894_2012_1674_MOESM1_ESM.doc (84 kb)
ESM 1 (DOC 84 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Emilio L. Angelina
    • 1
  • Darío J. R. Duarte
    • 1
  • Nélida M. Peruchena
    • 1
    Email author
  1. 1.Laboratorio de Estructura Molecular y Propiedades, Área de Química Física, Departamento de Química, Facultad de Ciencias Exactas y Naturales y AgrimensuraUniversidad Nacional del NordesteCorrientesArgentina

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