  Experimental and theoretical studies of the unoccupied electronic structure
of CaCu2O3 single crystals have been performed using polarization-dependent
x-ray absorption spectroscopy and band structure calculations. The measured
hole distribution shows an unusual large number of holes in orbitals parallel
to the interlayer direction which is in agreement with the theoretical
analysis. CaCu2O3 deviates significantly from the standard pd-sigma cuprate
picture. The corresponding strong interlayer exchange is responsible for the
missing spin gap generic for other two-leg ladder cuprates.
