We report photoelectron spectroscopy studies of the valence band struc
ture of the layered compounds TiS2, ZrSe2, and VSe2, and of changes in
duced by in situ intercalation with Cs. The pure compounds crystallize
with the same structure, the 1T-CdI2 structure, but their electronic
properties are different; TiS2 is a narrow-gap semiconductor (E(g) sim
ilar to 0.2 eV), ZrSe2 is a semiconductor (E(g) similar to 1 eV) and V
Se2 is a semimetal. Despite their different electronic properties, the
results show that the character of their valence bands changes from 3
D to 2D upon intercalation with Cs. The observed changes, supported by
LAPW band calculations, go far beyond the rigid band model.