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Introduction to Structural Chemistry pp 227–274Cite as

Intermolecular Forces

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Abstract

Three types of intermolecular interactions are considered: van der Waals (vdW), donoracceptor and hydrogen bonds. Are vdW forces caused by instantaneous dipoles created by electrons’ orbiting the nuclei (London)—or by accumulation of electron density between atoms (Feynman, later Bader), broadly similar to covalent bonding? Is crystal packing governed by the closest contacts—or by diffuse interactions of more distant atoms? What is the physical meaning of vdW radii? Are they additive, iso- or anisotropic, and how they relate to atom-atom potential curves? What is special about condensed helium? These and other issues are discussed invoking structures of crystals and of gas-phase dimers (vdW molecules), equations of state, thermal motion, electron density maps, and polarizabilities. There is a correspondence, both in energy and geometry, between covalent and vdW bonding, whereas donor-acceptor interactions are intermediate between them. Hydrogen bonds are reviewed briefly, clearing some common misconceptions which over-estimate their importance.

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Author information

Authors and Affiliations

  1. Institute of Struct. Macrokinetics and Materials Science, Russian Academy of Sciences, Academician Osipyan str. 8, 142432, Chernogolovka, Moscow Region, Russia

    Prof. Stepan S. Batsanov

  2. Chemistry Department, Durham University, Science Site, South Road, DH1 3LE, Durham, United Kingdom

    Andrei S. Batsanov Ph.D.

Authors
  1. Prof. Stepan S. Batsanov
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  2. Andrei S. Batsanov Ph.D.
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Correspondence to Stepan S. Batsanov .

Appendices

Appendix

4.1.1 Supplementary Tables

Table S4.1 Bond energies E (J/mol) and deviations from additive values in molecules of rare gases (From the review [4.1] and original papers, independent measurements are averaged DE = ½[E(Rg·Rg) + E(Rg′ Rg′)] − E exp(Rg Rg′))
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Table S4.2 Bond energies (kJ/mol) in van der Waals molecules RgM
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Table S4.3 Bond energies (kJ/mol) in van der Waals complexes of atom · molecule type
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Table S4.4 Bond energies (kJ/mol) in van der Waals moleculemolecule/atom complexes
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Table S4.5 Bond energies (kJ/mol) in atomion type complexes
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Table S4.6 Bond energies (kJ/mol) in ion molecule type complexes
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Table S4.7 Interatomic distances (Å) in van der Waals molecules A · Rga
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Table S4.8 Distances (Å) between centers of mass in van der Waals complexes Rg · AnBm and Hg · AnBm
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Table S4.9 Distances Rg···M (Å) in van der Waals complexes Rg · MXa
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Table S4.10 Distances d(Å) in van der Waals complexes comprising two molecules, The distance between molecules’ centers of mass, except where specified, (X = halogen atom)
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Table S4.11 Van der Waals radii of nonmetals, determined by X-ray analysis from 1939 to 2005
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Table S4.12 The van der Waals radii (Å) of metals, calculated from structural data
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Table S4.13 Crystallographic van der Waals radii (Å) of metals
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Table S4.14 Quantum mechanical vdW equilibrium radii (Å) of selected elements
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Table S4.15 The molecular mechanics equilibrium radii (Å) of selected elements
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Table S4.16 The equilibrium vdW radii (Å) of elements according to Allinger [4.186] (upper lines) and Batsanov (middle [4.175] and lower [4.176] lines)
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Table S4.17 The anisotropic vdW radii of H and X in solid-state HX molecules [4.190]
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Table S4.18 The optical anisotropy, the length of bonds and the anisotropic vdW radii of X in X2/AXn molecules (in Å) [4.191]
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Table S4.19 Lengths and energies of the donor-acceptor and normal chemical metal-nitrogen bonds
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Table S4.20 Interatomic distances (Å) in the О–Н···О system
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Table S4.21 Crystallographic parameters of the ice crystal structures [4.195]
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Batsanov, S., Batsanov, A. (2012). Intermolecular Forces. In: Introduction to Structural Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-4771-5_4

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