Molecular limits to the quantum confinement model in diamond clusters.
The electronic structure of monodispersed, hydrogen-passivated diamond clusters (diamondoids) in the gas phase has been studied with x-ray absorption spectroscopy. The data show that the bulk-related unoccupied states do not exhibit any quantum confinement. Additionally, density of states below the bulk absorption edge appears, consisting of features correlated to CH and CH2 hydrogen surface termination, resulting in an effective redshift of the lowest unoccupied states. The results contradict the commonly used and very successful quantum confinement model for semiconductors, which predicts increasing band edge blueshifts with decreasing particle size. Our findings indicate that in the ultimate size limit for nanocrystals a more molecular description is necessary.