Physisorption of helium on a TiO2(110) surface: Periodic and finite cluster approaches

Abstract

As a proto-typical case of physisorption on an extended transition-metal oxide surface, the interaction of a helium atom with a TiO2(110)-(1×1) surface is studied here by using finite cluster and periodic approaches and both wave-function-based (post-Hartree–Fock) quantum chemistry methods and density functional theory. Both classical and advanced finite cluster approaches, based on localized Wannier orbitals combined with one-particle embedding potentials, are applied to provide (reference) coupled-cluster and second-order Möller–Plesset interaction energies. 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 a subsequent simulation of helium mediated deposition on oxide surfaces.