V-V Bond-Length Fluctuations in Vox

TL;DR

This paper investigates how cooperative vanadium-vanadium bond-length fluctuations in VOx significantly suppress phonon thermal conductivity, linking structural dynamics to electronic and thermal properties.

Contribution

It proposes a novel model attributing thermal conductivity suppression in VOx to V-V bond-length fluctuations, extending understanding of transition-metal oxides.

Findings

Stronger phonon suppression than expected from vacancies alone

Bond-length fluctuations explain pseudogap and magnetic susceptibility behavior

Model accounts for thermal and structural anomalies in VOx

Abstract

We report a significantly stronger suppression of the phonon contribution to the thermal conductivity in VOx than can be accounted for by disorder of the 16 % atomic vacancies present in VO. Since the transition from localized to itinerant electronic behavior is first-order and has been shown to be characterized by bond-length fluctuations in several transition-metal oxides with the perovskite structure, we propose that cooperative V-V bond-length fluctuations play a role in VO similar to the M-O bond-length fluctuations in the perovskites. This model is able to account for the strong suppression of the thermal conductivity, the existence of a pseudogap confirmed by thermoelectric power, an anomalously large Debye-Waller factor, the temperature dependence of the magnetic susceptibility, and the inability to order atomic vacancies in VO.