Adsorption and reconstruction of metal-phthalocyanine molecules on Pt(001) investigated by density functional theory

The adsorption and reconstruction of M-phthalocyanine (MPc) (M = Co, Li, Mg, Pb, Pt, Si, Sn and Zn) molecules on Pt(001) are investigated by density functional theory (DFT). We find that molecules only anchor on the hollow site with well-marked corrugation in surface normal. Molecular orientation on Pt(001) depends on the substrate rather than the metal type of MPc molecules. At stable state, MPc takes two enantiomorphous adsorbing structures, which corresponds to molecules rotating clockwise and anticlockwise by 24.3 (± 0.1°) relative to Pt[110] direction. Owing to molecule-substrate interaction, achiral MPcs become chiral accompanied by symmetry decreasing from D4h of planar MPcs and C4v of nonplanar MPcs to C4. The metal type of MPcs has significant effect on their potential applications and the quantity of charge transfer from substrate. In addition, we predict surface reconstructions induced by MPc molecule adsorption, which is consistent with recent experimental studies.