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Dihydrogen Bonds: Novel Feature of Hydrogen Bond Interactions

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Practical Aspects of Computational Chemistry

Abstract

The term dihydrogen bond (DHB) describes two hydrogen atoms being usually in contact closer than the corresponding sum of van der Waals radii. One of the hydrogen atoms is negatively charged while the second has a positive charge. This type of interaction was found in the crystal structures of metal-organic compounds in the middle of 1990s. There has been a vast number of theoretical and experimental studies on DHBs. Generally, it is the interaction between the Lewis acid and the Lewis base, similarly as a hydrogen bond (HB). Numerous investigations show that the DHB can be considered as a special type of HB since the analyses of energetic, geometrical, and topological parameters show similarities between both types of interactions.

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Notes

  1. 1.

    The hydrogen bond energy possesses a negative value and more negative value indicates stronger interaction. However, very often, for the convenience of explanations the absolute values are given in the texts. The same concerns the ranges of the energies given here, the positive values will be given hereafter through the whole text. The true negative values are included in tables and figures.

  2. 2.

    The attractive electrostatic interactions are proportional to ~R −2 and the van der Waals ones to ~R  − 6 (R is the distance between the interacting species). Hence, the electrostatic interactions “converge to zero” much slower than the van der Waals interactions.

  3. 3.

    This is discussed in the next sections.

  4. 4.

    These linear systems are often not in local minima. However, the recent studies (Grabowski et al., in preparation) show that the complexes being in minima are very close, in geometry and energy, to the linear structures.

  5. 5.

    MP4/aug-cc-pVTZ level of approximation.

  6. 6.

    It was mentioned earlier that the dispersion interaction energy (DIS) is the most important attractive term of the correlation energy (CORR); it is usually attributed to the van der Waals interactions, physical meaning of the latter is usually the sum of attraction (DIS) and the repulsive exchange energy (EX).

  7. 7.

    The calculations of (1Z)-2-borylethen-1-ol were performed at the MP2/6-311++G(d,p) level of approximation

  8. 8.

    There are also H–H stabilizing interactions [26] not classified as the Lewis acid–Lewis base ones and being different in nature than DHBs, H–H interactions often concern C–H···H–C systems (like for example in diphenyl molecule).

  9. 9.

    There is the O–H proton donating bond (of Cl2OH+ ion) and −δH acceptor (the BeH2 molecule).

  10. 10.

    These values, as well as H···H distance, for the Cl2OH···HBeH complex were obtained at the MP2/aug-cc-pVTZ//MP2/aug-cc-pVDZ level of approximation (BSSE correction included).

  11. 11.

    The calculations were performed at the MP2/aug’-cc-pVTZ level of approximation.

  12. 12.

    MP2/6-311++G(d,p) level calculations were carried out.

  13. 13.

    This is the exponential relationship which only roughly expresses the dependence. Since electron density at BCP ( ρ C) and the proton – acceptor distance may be treated as rough measures of the strength of interaction thus such correlation was found. To analyze the sample of complexes in detail, one should take into account ln( ρ C) to observe the possible sub-samples of all species taken into account.

  14. 14.

    The calculations were carried out up to MP2/aug-cc-pVQZ level of approximation.

  15. 15.

    The calculations were performed at MP2/aug-cc-pVTZ level of approximation.

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Acknowledgments

The authors thank for support from the NSF CREST Interdisciplinary Nanotoxicity Center (grant number HRD-0833178).

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Authors and Affiliations

  1. NSF CREST Interdisciplinary Nanotoxicity Center, Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS, 39217, USA

    Sławomir J. Grabowski & Jerzy Leszczynski

  2. Department of Chemistry, University of Łódź, 90-236, Łódź, ul.Pomorska, 149/153, Poland

    Sławomir J. Grabowski

Authors
  1. Sławomir J. Grabowski
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  2. Jerzy Leszczynski
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Correspondence to Jerzy Leszczynski .

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Editors and Affiliations

  1. Dept. Chemistry, Jackson State University, J. R. Lynch St. 1325, Jackson, 39217, U.S.A.

    Jerzy Leszczynski

  2. Dept. Chemistry, Jackson State University, J. R. Lynch St. 1325, Jackson, 39217, U.S.A.

    Manoj K. Shukla

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Grabowski, S.J., Leszczynski, J. (2009). Dihydrogen Bonds: Novel Feature of Hydrogen Bond Interactions. In: Leszczynski, J., Shukla, M. (eds) Practical Aspects of Computational Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-2687-3_12

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