Electronic Structure of Vanadium Dioxide: Ab initio Density Functional Theory Studies of Periodic and Local Systems

Abstract

The electronic structure of vanadium dioxide in its monoclinic and tetragonal (rutile) phase are calculated using the ab initio FP-LAPW method. Both VO 2 phases yield very similar band structures and densities of states (DOS) as expected from their structural similarity. A comparison of theoretical band dispersions of tetragonal VO 2 with recent angular resolved photoemission data yields very good agreement, which confirms the reliability of the FP-LAPW method to account for electronic dispersions in the present systems. The calculations yield metallic behavior for both VO 2 phases in contrast to experimental findings of the monoclinic phase being a small gap semiconductor. This discrepancy is explained by missing correlation contributions in the density functional theory (DFT) scheme used in the calculations. The DOS curves of the bulk systems are compared with the DOS of VO 2 (011) surface clusters obtained by DFT calculations and yield very close similarity in the O 2p band region without surface specific features which remains to be explained.

Modification of Electronic Properties of Mo2C Catalyst by Potassium Doping: Impact on the Reactivity in Hydrodenitrogenation Reaction of Indole

“…The calculations were performed within the Kohn−Sham formalism implemented in the DMol-960 program (InsightII release 95.0, Biosym/MSI, San Diego, 1995) using local density approximation with the VWN correlation-exchange potential and DNP basis set (double numerical augmented by polarization functions). Such an approach has been successfully used for the calculations of the band and the density of states (DOS) structures for the number of solids, such as transition-metal oxides, sulfides, and carbides, and it has been found that the replacement of LDA by gradient-corrected GGA functionals gave essentially the same results.…”

Synthetic paramontroseite VO2 with good aqueous lithium–ion battery performance

“…Comparing these calculation results with those for rutile and monoclinic VO 2 , it is found that the DOS of rutile VO 2 also possesses a continuous DOS around the Fermi level while the DOS of monoclinic VO 2 has a 0.1 eV wide deep minimum just above e F with a separated band. 5 Therefore, the characteristics of DOS and energy bands for paramontroseite VO 2 are quite similar to those of the metallic rutile VO 2 phase, rather than that of the semiconducting monoclinic VO 2 phase. This similarity of calculation results between the paramontroseite VO 2 and metallic rutile VO 2 phase thus provides further evidence for the metallic behavior of the paramontroseite VO 2 structure.…”

Structural and electrochemical behaviour of sputtered vanadium oxide films: oxygen non-stoichiometry and lithium ion sequestration

“…Several theoretical investigations (Carathers et al 1973;Bullet 1980;Mattheis 1994;Eyert and Hock 1998;Kurmaer et al 1998;Ven et al 1998;Hermann et al 2001;Herbert et al 2002) have addressed the problem of the resulting electronic band structures both in V 2 O 5 and in other vanadium oxides. Density functional approach has been particularly heavily employed (Eyert and Hock 1998;Hermann et al 2001). But our focus here is to obtain a qualitative understanding of the band structure alterations resulting from lithiation of V 2 O 5 and V 2 O 4⋅6 films based on molecular orbital (MO) approach.…”