We have measured the APS and XPS spectra of V2O5(V6O13). The time variation of the APS spectrum indicates that the chemical composition of the sample gradually changes during electron bombardment. A comparison between our APS and XPS spectra, and the literature data on XES, XAS, and the energy level diagram of molecular orbitals obtained by a cluster model calculation, illustrates the local breakdown of the one-particle orbital model of the solid.