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A benchmark for the non-covalent interaction (NCI) index or… is it really all in the geometry?

  • Julia Contreras-GarcíaEmail author
  • Roberto A. Boto
  • Fernando Izquierdo-Ruiz
  • Igor Reva
  • Tatiana Woller
  • Mercedes Alonso
Regular Article
Part of the following topical collections:
  1. Festschrift in honour of A. Vela

Abstract

Describing non-covalent interactions (NCIs) has shown to be of paramount importance in many areas of theoretical chemistry and related disciplines, such as biochemistry and material science. However, non-covalent interactions are subtle effects, very difficult to reproduce from most common computational approaches. Electron density studies have shown to provide a good semiquantitative visual approach to such interactions, which are much less prone to method dependency. But to which extent? This is the question addressed in this contribution. The NCI approach based on the reduced density gradient is given the third degree so as to provide the user with a benchmark on how it is affected by the computational method and the basis set of choice. We have assessed the dependence of the NCI results on the geometry. This last question is addressed in detail to dissect how, why and when the NCI method can be used to understand dispersion interactions. Along various examples, we will show that the NCI index is very little dependent on the method and basis set used in the calculation of the electron density as long as the geometry is kept fixed. Indeed, the biggest variations in NCI come from changes in the geometry. Thus, methods which provide descriptions of a given interaction type of different accuracies will yield different electron density organizations. This gives no qualitative variations in the NCI 3D picture. But it is reflected in quantitative NCI measures even in very subtle cases. Moreover, in the case of a failure of the calculation method, NCI can also reveal the sources of its error. NCI volumes are able to locate the energetic ordering in various conformational situations, but always in a relative manner. Absolute values should not be used in comparisons, nor between compounds that do not belong to the same family.

Keywords

Non-covalent interactions Benchmark NCI Electron density 

Notes

Acknowledgments

We want to thank Prof. Rzepa for useful discussions and his always present metadata which make research so much easier. This work was supported partially by the framework of CALSIMLAB under the public Grant ANR-11-LABX-0037-01 overseen by the French National Research Agency (ANR) as part of the “Investissements d’Avenir” program (Reference: ANR-11-IDEX-0004-02). FIR thanks to FPU program from MECD for a Ph.D. Grant and financial support from Spanish Ministerio de Economia y Competitividad and FEDER programs under Projects No. CTQ2012-35899-C02 and No. CTQ2015-67755-C2. M. A. thanks the Fund for Scientific Research−Flanders (FWO-12F4416N) for a postdoctoral fellowship and the Free University of Brussels (VUB) for financial support. The Coimbra Chemistry Centre (CQC) is supported by the Portuguese Fundação para a Ciência e a Tecnologia (FCT), through the Project UI0313/QUI/2013, co-funded by COMPETE-UE. I. R. acknowledges FCT for the Investigador FCT Grant.

Supplementary material

214_2016_1977_MOESM1_ESM.pdf (2.4 mb)
Supplementary material 1 (pdf 2503 KB)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Julia Contreras-García
    • 1
    Email author
  • Roberto A. Boto
    • 1
    • 2
  • Fernando Izquierdo-Ruiz
    • 3
  • Igor Reva
    • 4
  • Tatiana Woller
    • 5
  • Mercedes Alonso
    • 5
  1. 1.UMR 7616, Laboratoire de Chimie ThéoriqueSorbonne Universités, UPMC Univ Paris 06 & CNRSParisFrance
  2. 2.ICSSorbonne Universités, UPMC Univ Paris 06ParisFrance
  3. 3.Departamento de Química Física y AnalíticaUniversidad de OviedoOviedoSpain
  4. 4.CQC, Department of ChemistryUniversity of CoimbraCoimbraPortugal
  5. 5.ALGC Research Group General Chemistry (ALGC)Vrije Universiteit Brussel (VUB)BrusselsBelgium

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