The electronic structure of cobalt(II) phthalocyanine adsorbed on Ag(111)

The electronic states of submonolayers and multilayers of cobalt(II) phthalocyanine (CoPc) adsorbed on Ag(111) were examined with photoelectron spectroscopy to obtain insight into the details of the substrate-adsorbate interaction. UV photoelectron spectroscopy (UPS) reveals the presence of two interaction-related valence states in the direct vicinity of the Fermi edge, in agreement with previous DFT calculations. X-ray photoelectron spectra indicate that the substrate-adsorbate interaction results in transfer of electron density from the substrate to the Co(II) ion. Substantial changes in the Co 2p multiplet structure, a spectral pattern induced by the open-shell character of the central Co(II) ion, indicate a complete quenching of the molecular spin. While pristine CoPc molecules are paramagnetic with S = 1/2, molecules in direct contact to the Ag(111) substrate appear to be in a diamagnetic state.

Graphical abstractDownload high-res image (197KB)Download full-size imageHighlights► Co phthalocyanine on Ag(111) was studied with photoelectron spectroscopy (XPS/UPS). ► Co-Ag interaction evident from valence electronic structure and core level shifts. ► Adsorption-induced changes of Co 2p multiplet structure and spin-orbit splitting. ► Co 2p signal changes consistent with electron transfer from Ag substrate to Co ion.