The adsorption of noble gases onto TiO2(110), graphene, and metallic surfaces has been receiving strong attention during the last few years [1-7]. Besides being stereotypical dispersion-dominated systems in surface science, noble gases are utilized as carriers for soft-landing deposition [2,4,5] and as reporters to monitor the photocatalytic properties of titanium dioxide [8]. We examined the adsorption of weakly bound noble gases (Ne, Ar, Kr and Xe) onto the TiO2(110) surface using different van der Waals-corrected DFT-based treatments. The assessment of their performance is assisted by experimentally-based determinations of the adsorption energies [8], and the application of periodic Hartree-Fock and non-periodic DFT-based symmetry adapted perturbation theories. The most reliable results are provided by the revPBE-D3 approach: it produces adsorption energies that are within 3% of the experimental values for noble-gas atoms heavier than neon and attractive long-range tails which are consistent with our ab-initio benchmarking. Moreover, the revPBE density functional describes the short-range part of the potential energy curve more precisely, avoiding the exchange-only binding effects of the PBE functional. The non-local vdW-DF2 density functional performs well at the long-range potential region but largely overestimates the adsorption energies of noble gas atoms as light as argon. When applied without incorporating the screening between fluctuating dipoles, the Tkatchenko-Scheffler method produces long-range attractive tails that decay too slowly, as in first-generation non-local vdW-DF density functional. References [1] M. P. de Lara-Castells, N. F. Aguirre, A. O. Mitrushchenkov, Chem. Phys. 399 (2012) 272. [2] N. F. Aguirre, D. Mateo, A. O. Mitrushchenkov, M. Pi, M. P. de Lara-Castells, J. Chem. Phys. 136 (2012) 124703. [3] M. P. de Lara-Castells, H. Stoll, A. O. Mitrushchenkov, J. Phys. Chem. A 118 (2014) 6367. [4] M. P. de Lara-Castells, N. F. Aguirre, H. Stoll, A. O. Mitrushchenkov, D. Mateo, M. Pi, J. Chem. Phys. 142 (2015) 131101. [5] M. P. de Lara-Castells, H. Stoll, B. Civalleri, M. Causà, E. Voloshina, A. O. Mitrushchenkov, and M. Pi, J. Chem. Phys. 141 (2014) 151102. [6] M. P. de Lara-Castells, M. Bartolomei, A. O. Mitrushchenkov, H. Stoll, J. Chem. Phys., submitted. [7] R. Grenier, Q. -D. To, M. P. de Lara-Castells, C. Leonard, J. Phys. Chem A 119 (2015) 6897. [8] N. G. Petrik, G. A. Kimmel, Phys. Chem. Chem. Phys. 16 (2014) 2338.

Noble gas adsorption on the TiO2(110) surface: An ab-initio-assisted venture in van der Waals-corrected DFT

251st National Meeting (2016)

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