Electronic and vibrational properties of vanadium-carbide nanowires

Abstract

We have made an effort to understand the properties of transition metal carbide nanowires (NWs) and studied vanadium-carbide (VC) nanowires as a specific case. Different structures have been considered and their electronic and vibrational properties studied employing density functional theory. The effect of dimensionality is very well brought forth by these NWs, narrow/thinner structures have clear preference for magnetic state with sizeable magnetic moment at the V sites. As the thickness/width increases, the margin decreases and the magnetic moment disappears altogether for structures like square and rectangular NWs. The cohesive energy per atom increases with the increase in lateral dimensions of the NW, and it is about 88% of the bulk value for the rectangular NW, while it is only 50% for the linear chain. All the wires are conducting in nature, with the linear and zigzag wires having half-metallic character. Our calculations show that the V atoms decide the electronic and magnetic properties in these while compressibility, a mechanical property, is governed by the C atoms. The electron localization function beautifully illustrates the closeness of thicker/wider NWs to the bulk. It also reveals that electrons are highly localized around C atoms; however, the amount of charge transferred depends strongly on the structure of wire. The optical properties unfurl the impact of different spatial expanse in the cross section of NW in a nice way, e.g., ε2xx > ε2yy (ε2 is imaginary part of dielectric function) for all those with a larger expanse along X compared to Y and vice-versa. Thicker nanowires seem to be more suitable for optical applications. Site-resolved phonon density of states shows that presence of C atoms is responsible for high frequency branches. The heat capacity variation for various structures closely follows the magnitude of respective phonon density of states.