On the dual character of charged metal-molecule hybrids and the opposite behaviour of the forward and reverse CT processesElectronic supplementary information (ESI) available: Computational details and tables and figures mentioned in the text. See DOI: 10.1039/c4cp03984j

DFT calculations predict two different electronic structures of metal-molecule hybrids which are selected depending on the surface charge. While the metal-to-molecule CT states are very sensitive to the charge, the energies of the reverse molecule-to-metal CT processes are surprisingly not modified at all by the charge of the metal. Charged molecules bonded to metals show two kinds of electronic structures depending on the charge of the metal.