Even though the semimetallic behavior of 1T-TiSe2 seemed to be well established by band structure calculations and photoemission results, this conclusion has been challenged recently. Two high-resolution photoemission investigations deduced semiconducting behavior, however with a very small band gap. Such conclusion from photoemission is afflicted, in principle, by the problem of determining an unoccupied conduction band by photoemission. This problem is solved here by the idea of H2O adsorption onto the van der Waals-like surface, causing a distinct bending of the bands and resulting in a filled lowest conduction band. The detailed analysis yields undoubtedly semiconducting behavior for 1T-TiSe2 and interesting properties of a semiconductor with extremely small band gap.
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