The electronic structure and chemical bonding in alpha-TeO2 are invest
igated by x-ray-photoemission spectroscopy and first-principles cluste
r calculations. The calculated valence-band spectrum is in good agreem
ent with the experimental one. The partial-density-of-states analysis
shows an s-p hybrid on a Te atom in the bonding between Te and O atoms
. Mulliken overlap populations indicate that four strong and two relat
ively weak Te-O bonds are formed around the Te atom.