  We report the results of a comprehensive spectroscopic ellipsometry study of
NaCu2O2, a compound composed of chains of edge-sharing Cu2+O4 plaquettes and
planes of Cu1+ ions in a O-Cu1+-O dumbbell configuration, in the spectral range
0.75-6.5 eV at temperatures 7 -300 K. The spectra of the dielectric function
for light polarized parallel to the Cu1+ planes reveal a strong in-plane
anisotropy of the interband excitations. Strong and sharp absorption bands
peaked at 3.45 eV (3.7 eV) dominate the spectra for polarization along
(perpendicular) to the Cu2+O2 chains. They are superimposed on flat and
featureless plateaux above the absorption edges at 2.25 eV (2.5 eV). Based on
density-functional calculations, the anomalous absorption peaks can be assigned
to transitions between bands formed by Cu1+ 3dxz(dyz) and Cu2+ 3dxy orbitals,
strongly hybridized with O pstates. The major contribution to the background
response comes from transitions between Cu1+ 3dz2 and 4px(py) bands. This
assignment accounts for the measured in-plane anisotropy. The dielectric
response along the Cu2+O2 chains develops a weak two-peak structure centered at
2.1 and 2.65 eV upon cooling below 100 K, along with the appearance of spin
correlations along the Cu2+O2 chains. These features bear a striking
resemblance to those observed in the single-valent Cu2+O2 chain compound
LiCuVO4, which were identified as an exciton doublet associated with
transitions to the upper Hubbard band that emerges as a consequence of the
long-range Coulomb interaction between electrons on neighboring Cu2+ sites
along the chains. An analysis of the spectral weights of these features yields
the parameters characterizing the on-site and long-range Coulomb interactions.
