Utecht Manuel, Pan Tianluo, Klamroth Tillmann, Palmer Richard E
Institut für Chemie, Universität Potsdam , Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam-Golm, Germany.
J Phys Chem A. 2014 Aug 21;118(33):6699-704. doi: 10.1021/jp504208d. Epub 2014 Jun 20.
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.
受近期原子操纵实验的启发，我们报告了氯苯在Si(111)-7×7表面化学吸附和物理吸附极小值的量子化学计算。采用密度泛函理论簇方法，使用B3LYP杂化泛函并结合Grimme的经验色散校正（D3）。我们能够识别出结合能为1.6 eV的化学吸附位点和0.6 eV的物理吸附能，这两者都与实验数据趋势吻合良好。簇方法为基于第一性原理对该系统进行扫描隧道显微镜操纵实验的动力学描述开辟了可能性，该实验的解释涉及化学吸附态和物理吸附态。然而，我们发现对于簇的选择、基组以及色散校正的评估必须格外小心。
