Most of the cases aggregation leads to red shift in absorption band gap. This phenomenon is more prominent in the case of Au-semiconductor heterostructures but Ag aggregates does not show much more red shift in Ag-semiconductor heterostructures. Any one can give me explanation what would be the possible reasons?
Thank you
Are you referring to Ag+ and Au+ complexes? If yes, Ag+ is a closed shell 4d10 system, that when excited electronically to the 4d9 5s1 state, is more likely to experience repulsion in the excited singlet state leading to a blue shift; see the case of the Dewar-Chat effect first documented in the UV-Vis in binding Ag+ and ethylene in the paper attached (Fig. 3). In Au+ complexes, the closed shell 5d10 system when excited to 5d9 6s1 has a 6s1 that is buried within the 5d shell electrons and is less susceptible to repulsion interactions with ligands.
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