Workshop CMST Action CM1200 CODECS: Holistic Computational Spectroscopy, 16-18 November 2011, Pisa, Italy. http://codecs.sns.it/index.php/Holistic_Computational_SpectroscopyAs a proto-typical case of physisorption on an extended transition-metal oxide surface, the interaction of a helium atom with a TiO2(110) surface is studied here by using finite cluster and periodic approaches and both wavefunction-based (post Hartree-Fock) quantum chemistry methods, as well as density functional theory. The finite cluster approach is applied to provide reference results at coupled-cluster and perturbative second-order Möller-Plesset levels of theory. It is shown that once the basis set is specifically tailored to minimize the basis set superposition error, periodic calculations using the Perdew Burke-Ernzerhof functional yield short and medium-range interaction potentials in very reasonable agreement with those obtained using the correlated wave-function-based methods, while small long-range dispersion corrections are necessary to reproduce the correct asymptotic behavior. This study is aimed at the simulation of helium droplet-mediated deposition of metallic clusters on oxide surfaces.Peer Reviewe
