Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

Journal Article · Fri Nov 14 00:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4898356· OSTI ID:22310799

Al-Hamdani, Yasmine S.; Michaelides, Angelos ^[1]; Alfè, Dario ^[1]; Lilienfeld, O. Anatole von ^[2]

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1. Thomas Young Centre and London Centre for Nanotechnology, 17–19 Gordon Street, London WC1H 0AH (United Kingdom)
2. Institute of Physical Chemistry, Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel (Switzerland)

Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B{sub 3}N{sub 3}H{sub 6}) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.

• OSTI ID: 22310799
• Journal Information: Journal of Chemical Physics, Vol. 141, Issue 18; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BENZENE
DENSITY FUNCTIONAL METHOD
DIFFUSION
DOPED MATERIALS
ELECTRONIC STRUCTURE
GRAPHENE
INTERACTIONS
MOLECULES
MONOMERS
MONTE CARLO METHOD
SURFACES
VAN DER WAALS FORCES
WATER