We have measured the V 2p(3/2) and O 1s X-ray absorption spectra of si
ngle crystal V2O5 and V6O13 and compared to linear combinations of ato
mic orbitals (LCAO) density of slates (DOS) calculations. The spectra
change dramatically with incident angle. The use of polarized light an
d a single crystal limits the number of transitions possible, revealin
g spectral features that cannot be resolved on polycrystals (angle-int
egrated). The measured O 1s and V 2p(3/2) spectra agree with the proje
cted unoccupied O 2p and V 3d DOS, respectively, indicating that atomi
c and solid state effects, including V-O hybridization, must be includ
ed to describe adequately the spectra.