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The roles of charge transfer and polarization in non-covalent interactions: a perspective from ab initio valence bond methods

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Abstract

Noncovalent interactions are ubiquitous and have been well recognized in chemistry, biology and material science. Yet, there are still recurring controversies over their natures, due to the wide range of noncovalent interaction terms. In this Essay, we employed the Valence Bond (VB) methods to address two types of interactions which recently have drawn intensive attention, i.e., the halogen bonding and the CH‧‧‧HC dihydrogen bonding. The VB methods have the advantage of interpreting molecular structures and properties in the term of electron-localized Lewis (resonance) states (structures), which thereby shed specific light on the alteration of the bonding patterns. Due to the electron localization nature of Lewis states, it is possible to define individually and measure both polarization and charge transfer effects which have different physical origins. We demonstrated that both the ab initio VB method and the block-localized wavefunction (BLW) method can provide consistent pictures for halogen bonding systems, where strong Lewis bases NH3, H2O and NMe3 partake as the halogen bond acceptors, and the halogen bond donors include dihalogen molecules and XNO2 (X = Cl, Br, I). Based on the structural, spectral, and energetic changes, we confirm the remarkable roles of charge transfer in these halogen bonding complexes. Although the weak C-H∙∙∙H-C interactions in alkane dimers and graphane sheets are thought to involve dispersion only, we show that this term embeds delicate yet important charge transfer, bond reorganization and polarization interactions.

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Adapted from Fig. 6 in Ref. [75], with ACS permission. Copyright 2013

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Acknowledgements

SS acknowledges the support from the ISF (grant number 520/18). This work was performed in part at the Joint School of Nanoscience and Nanoengineering, a member of the Southeastern Nanotechnology Infrastructure Corridor (SENIC) and National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (Grant ECCS-2025462).

Funding

The Israel Science Foundation (ISF, grant number 520/18); the National Science Foundation of US (NSF, Grant ECCS-2025462).

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Authors and Affiliations

  1. Department of Nanoscience, Joint School of Nanoscience and Nanoengineering, University of North Carolina at Greensboro, Greensboro, NC, 27401, USA

    Yirong Mo

  2. Institute of Chemistry, The Hebrew University of Jerusalem, 9190407, Jerusalem, Israel

    David Danovich & Sason Shaik

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  1. Yirong Mo
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  2. David Danovich
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  3. Sason Shaik
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YM and SS organized the project and wrote together; DD performed computations.

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Correspondence to Yirong Mo or Sason Shaik.

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The original online version of this article was revised due to the word “graphane” was misspelled as “graphene” in multiple places in text.

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Mo, Y., Danovich, D. & Shaik, S. The roles of charge transfer and polarization in non-covalent interactions: a perspective from ab initio valence bond methods. J Mol Model 28, 274 (2022). https://doi.org/10.1007/s00894-022-05187-8

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