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Transferability and accuracy by combining dispersionless density functional and incremental post-Hartree-Fock theories: Noble gases adsorption on coronene/graphene/graphite surfaces

Abstract : The accuracy and transferability of the electronic structure approach combining dispersionless density functional theory(DFT) [K. Pernal et al., Phys. Rev. Lett. 103, 263201 (2009)] with the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)], are validated for the interaction between the noble-gas Ne, Ar, Kr, and Xe atoms and coronene/graphene/graphite surfaces. This approach uses the method of increments for surface cluster models to extract intermonomer dispersion-like (2- and 3-body) correlation terms at coupled cluster singles and doubles and perturbative triples level, while periodic dispersionless density functionals calculations are performed to estimate the sum of Hartree-Fock and intramonomer correlation contributions. Dispersion energy contributions are also obtained using DFT-based symmetry-adapted perturbation theory [SAPT(DFT)]. An analysis of the structure of the X/surface (X = Ne, Ar, Kr, and Xe) interaction energies shows the excellent transferability properties of the leading intermonomer correlation contributions across the sequence of noble-gas atoms, which are also discussed using the Drude oscillator model. We further compare these results with van der Waals-(vdW)-corrected DFT-based approaches. As a test of accuracy, the energies of the low-lying nuclear bound states supported by the laterally averaged X/graphite potentials (X = 3He, 4He, Ne, Ar, Kr, and Xe) are calculated and compared with the best estimations from experimental measurements and an atom-bond potential model using the ab initio-assisted fine-tuning of semiempirical parameters. The bound-state energies determined differ by less than 6–7 meV (6%) from the atom-bond potential model. The crucial importance of including incremental 3-body dispersion-type terms is clearly demonstrated, showing that the SAPT(DFT) approach effectively account for these terms. With the deviations from the best experimental-based estimations smaller than 2.3 meV (1.9%), the accuracy of the combined DFT and post-HF incremental scheme is established for all the noble-gas atoms. With relative deviations smaller than 4% and 11%, good agreement is also achieved by applying the vdW-corrected DFT treatments PBE-D3 and vdW-DF2 for noble-gas atoms heavier than neon.
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https://hal-upec-upem.archives-ouvertes.fr/hal-01232150
Contributor : Alexander Mitrushchenkov <>
Submitted on : Monday, November 23, 2015 - 9:56:51 AM
Last modification on : Friday, June 19, 2020 - 7:52:04 PM

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María Pilar de Lara-Castells, Massimiliano Bartolomei, Alexander O. Mitrushchenkov, Hermann Stoll. Transferability and accuracy by combining dispersionless density functional and incremental post-Hartree-Fock theories: Noble gases adsorption on coronene/graphene/graphite surfaces. Journal of Chemical Physics, American Institute of Physics, 2015, 143 (19), pp.194701. ⟨10.1063/1.4935511⟩. ⟨hal-01232150⟩

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