title: Quantum chemical cluster models for chemi- and physisorption of chlorobenzene on Si(111)-7×7.
abstract: Motivated by recent atomic manipulation experiments, we report quantum chemical calculations for chemi- and physisorption minima of chlorobenzene on the Si(111)-7×7 surface. A density functional theory cluster approach is applied, using the B3LYP hybrid functional alongside Grimme's empirical dispersion corrections (D3). We were able to identify chemisorption sites of binding energies of 1.6 eV and physisorption energies of 0.6 eV, both in encouraging agreement with the trend of experimental data. The cluster approach opens up the possibility of a first-principles based dynamical description of STM manipulation experiments on this system, the interpretation of which involves both the chemi- and physisorbed states. However, we found that special care has to be taken regarding the choice of clusters, basis sets, and the evaluation of the dispersion corrections.
authors.affiliation: Institut für Chemie, Universität Potsdam , Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam-Golm, Germany.
authors.forename: Manuel
authors.initials: M
authors.lastname: Utecht
authors.forename: Tianluo
authors.initials: T
authors.lastname: Pan
authors.forename: Tillmann
authors.initials: T
authors.lastname: Klamroth
authors.forename: Richard E
authors.initials: RE
authors.lastname: Palmer