Abstract
Isomorphic titanium dichalcogenide TiX2 (X=S, Se, Te) compounds exhibit
very diverse and anisotropic chemical and physical properties. The
temperature dependent electrical resistivity of TiSe2 was found to
exhibit anomalous behavior at low temperatures (< 200 K) which
was connected to the emergence of a unique charge density wave (CDW),
which was explained on the basis of 2a0×c0 superstructure formation,
whereas bulk TiS2 and TiTe2 do not exhibit CDW instability. In order to
understand their diverse nature, we have systematically investigated the
electronic structure of titanium dichalcogenides by using the FPLAPW and
PAW methods based on the density functional theory (DFT). The energy
bands calculated by implementing the latest generalized gradient
approximation (GGA) with PBE and TB-mBJ potentials confirm the
semiconducting nature of TiS2 and metallic nature of TiSe2 and TiTe2,
however the Wu-Cohen potentials show a semi-metallic nature for all
three dichalcogenides. The diverse properties of TiX2 are governed by
two bands, S/Se/Te p-band close to the Γ-point and Ti 3d-band around M
(L)-points. The presence of electron and hole pockets at the Fermi
energy level have been previously confirmed experimentally, although our
calculated size and extent of overlap of these pockets was overestimated
compared to experiments. Various physical parameters such as electrical
conductivity, Seebeck coefficient etc. which depend sensitively on
nature of states at the Fermi level also amply illustrate the diversity
of the compounds. The electron localization function and Bader charge
partitioning illustrate the increasing covalency with varying
chalcogenide atom, which is consistent with the spectral features
observed in the DOS. The lattice dispersion of the titanium
dichalcogenides are calculated by using the PAW method with PBE
potentials. The phonon band structure is correlated to the electronic
band structure in order to explain the occurrence of CDW. In TiSe2, the
presence of a phonon mode with imaginary frequency indicated lattice
instability against distortion. The displacements of Ti-Se atoms of this
phonon mode allows the mixing of states of the electron and hole
pockets, which leads to lattice distortion i.e. a CDW structure which
lowers the energy of the system. Although there is a weak imaginary
mode, the mixing of states is absent in TiS2 due to absence of electron
or hole pockets, whereas TiTe2 is structurally most stable.