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

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Author Yasmine S. Al-Hamdani Dario Alfè O. Anatole von Lilienfeld and Angelos Michaeledis,
Project From atomistic exploration of chemical compound space towards bio-molecular design: Quantum mechanical rational compound design (QM-RCD)
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Original article (peer-reviewed)

Journal Journal of Chemical Physics
Volume (Issue) 141
Page(s) 18C530
Title of proceedings Journal of Chemical Physics
DOI 10.1063/1.4898356


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 (B3N3H6) 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.