Silver clusters molecular orbitals

The assignment that the emissions arise from a LMCT [E M4] excited state with mixing of a metal-centered d sjd p) state has been substantiated by ab initio and Fenske-Hall molecular orbital calculations performed for the silver(I) clusters. These results revealed that the HOMOs of the clusters are principally Ag—E bonding orbitals, while the LUMOs are metal-localized orbitals with predominantly 55 and 5p character. Furthermore, the calculated HOMO-LUMO energy gaps decrease in the order (13a) > (13b) > (13c), consistent with the observed trend for the emission energies of the complexes. 

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