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Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

Nature Reviews Chemistry volume 1, Article number: 0017 (2017) Cite this article

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An Erratum to this article was published on 22 March 2017

Abstract

Chemists generally believe that covalent and ionic bonds form much stronger links between atoms than the van der Waals force does. However, this is not always so. We present cases in which van der Waals dispersive forces introduce new competitive bonding possibilities rather than just modulating traditional bonding scenarios. Although the new possibilities could arise from any soft–soft chemical interaction, we focus on bonding between gold atoms and alkyl or arylsulfur ligands, RS. Consideration of all the interactions at play in sulfur-protected gold surfaces and gold nanoparticles is necessary to understand their structural, chemical and spectroscopic properties. In turn, such knowledge opens pathways to new chemical entities and innovative nanotechnological devices. Such experimentation is complemented by modern theory, and presented here is a broad overview of computational methods appropriate to fields ranging from gas-phase chemistry to device physics and biochemistry.

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Figure 1: Mechanisms by which van der Waals dispersion forces can modify chemical bonding.
Figure 2: Hard and soft acids and bases, and ionic, van der Waals and covalent bonding.
Figure 3: Frontier orbital interactions in some standard chemical bonding scenarios.
Figure 4: Diverse bonding motifs are possible when gold surfaces bind organosulfur ligands.
Figure 5: Synthetic pathways to Au(I) thiolates and Au(O) thiyls.

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Acknowledgements

Financial support from the Australian Research Council Discovery Projects grant DP160101301, and computational support from National Computational Infrastructure (d63 and no2) and INTERSECT (r88 and sb4) are gratefully acknowledged. The authors also acknowledge helpful discussions with J. Zhang and Q. Chi, Technical University of Denmark.

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  1. reimers@shu.edu.cn

  2. Jeffrey.Reimers@uts.edu.au

Authors and Affiliations

  1. International Centre for Quantum and Molecular Structures, College of Sciences, Shanghai University, Shanghai, 200444, China

    Jeffrey R. Reimers

  2. School of Mathematical and Physical Sciences, University of Technology Sydney, New South Wales, 2007, Australia

    Jeffrey R. Reimers & Michael J. Ford

  3. Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, 3086, Victoria, Australia

    Sebastian M. Marcuccio

  4. Advanced Molecular Technologies Pty Ltd, Unit 1, 7–11 Rocco Drive Scoresby, 3179, Victoria, Australia

    Sebastian M. Marcuccio

  5. Department of Chemistry, Technical University of Denmark, Kongens, 2800, Lyngby, Denmark

    Jens Ulstrup

  6. School of Chemistry F11, University of Sydney, New South Wales, 2006, Australia

    Noel S. Hush

  7. School of Molecular Bioscience, University of Sydney, New South Wales, 2006, Australia

    Noel S. Hush

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  1. Jeffrey R. Reimers
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Correspondence to Jeffrey R. Reimers.

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Reimers, J., Ford, M., Marcuccio, S. et al. Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles. Nat Rev Chem 1, 0017 (2017). https://doi.org/10.1038/s41570-017-0017

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