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

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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.

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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.

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Authors and Affiliations

  1. UMR 7616, Laboratoire de Chimie Théorique, Sorbonne Universités, UPMC Univ Paris 06 & CNRS, case courrier 137, 4 place, Paris, France

    Julia Contreras-García & Roberto A. Boto

  2. ICS, Sorbonne Universités, UPMC Univ Paris 06, 75005, Paris, France

    Roberto A. Boto

  3. Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain

    Fernando Izquierdo-Ruiz

  4. CQC, Department of Chemistry, University of Coimbra, Coimbra, Portugal

    Igor Reva

  5. ALGC Research Group General Chemistry (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels, Belgium

    Tatiana Woller & Mercedes Alonso

Authors
  1. Julia Contreras-García
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  2. Roberto A. Boto
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  3. Fernando Izquierdo-Ruiz
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  4. Igor Reva
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  5. Tatiana Woller
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  6. Mercedes Alonso
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Correspondence to Julia Contreras-García.

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Published as part of the special collection of articles “Festschrift in honour of A. Vela”.

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Contreras-García, J., Boto, R.A., Izquierdo-Ruiz, F. et al. A benchmark for the non-covalent interaction (NCI) index or… is it really all in the geometry?. Theor Chem Acc 135, 242 (2016). https://doi.org/10.1007/s00214-016-1977-7

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