We investigated the valence electronic structure of diamondoid particles in
the gas phase, utilizing valence photoelectron spectroscopy. The samples were
singly or doubly covalently bonded dimers or trimers of the lower diamondoids.
Both the bond type and the combination of bonding partners are shown to affect
the overall electronic structure. For singly bonded particles, we observe a
small impact of the bond on the electronic structure, whereas for doubly bonded
particles, the connecting bond determines the electronic structure of the
highest occupied orbitals. In the singly bonded particles a superposition of
the bonding partner orbitals determines the overall electronic structure. The
experimental findings are supported by density functional theory computations
at the M06-2X/cc-pVDZ level of theory.Comment: 7 pages, 7 figure
