Orbital- and kz -Selective Hybridization of Se 4p and Ti 3d States in the Charge Density Wave Phase of TiSe2

We revisit the enduring problem of the 2×2×2 charge density wave (CDW) order in TiSe2, utilizing photon energy-dependent angle-resolved photoemission spectroscopy to probe the full three-dimensional high- and low-temperature electronic structure. Our measurements demonstrate how a mismatch of dimensionality between the 3D conduction bands and the quasi-2D valence bands in this system leads to a hybridization that is strongly kz dependent. While such a momentum-selective coupling can provide the energy gain required to form the CDW, we show how additional "passenger" states remain, which couple only weakly to the CDW and thus dominate the low-energy physics in the ordered phase of TiSe2.