Adsorption-induced symmetry reduction of metal-phthalocyanines studied by vibrational spectroscopy

We investigate the vibrational properties of Pt- and Pd-phthalocyanine ( PtPc and PdPc) molecules on Ag(111) with high-resolution electron energy loss spectroscopy (HREELS). In the monolayer regime, both molecules exhibit long-range order. The vibrational spectra prove a flat adsorption geometry. The redshift of specific vibrational modes suggests a moderate interaction of the molecules with the substrate. The presence of asymmetric vibrational peaks indicates an interfacial dynamical charge transfer (IDCT). The molecular orbital that is involved in IDCT is the former E-g lowest unoccupied molecular orbital (LUMO) of the molecules that becomes partially occupied upon adsorption. A group-theoretical analysis of the IDCT modes, based on calculated vibrational frequencies and line shape fits, provides proof for the reduction of the symmetry of the molecule-substrate complex from fourfold D-4h to C-2v ( sigma(v)), Cs (sigma(v)), or C-2 and the ensuing lifting of the degeneracy of the former LUMO of the molecule. The vibration-based analysis of orbital degeneracies, as carried out here for PtPc/Ag(111) and PdPc/Ag(111), is particularly useful whenever the presence of multiple molecular in-plane orientations at the interface makes the analysis of orbital degeneracies with angle-resolved photoemission spectroscopy difficult.