Orbital reformation with vanadium trimerization in d² triangular lattice LiVO₂ revealed by ⁵¹V NMR

LiVO$_2$ is a model system of the valence bond solid (VBS) in $3d^2$ triangular lattice. The origin of the VBS formation has remained controversial. We investigate the microscopic mechanism by elucidating the $d$ orbital character via on-site $^{51}$V NMR measurements in a single crystal up to 550 K across a structural transition temperature $T_c$. The Knight shift, $K$, and nuclear quadrupole frequency, $\delta \nu$, show that the 3d orbital with local trigonal symmetry are reconstructed into a $d_{yz}d_{zx}$ orbital order below $T_c$. Together with the NMR spectra with three-fold rotational symmetry, we confirm a vanadium trimerization with $d$-$d$ $\sigma$ bonds. The Knight shift extracts the large Van-Vleck orbital susceptibility, $\chi^{\rm VV} = 3.6 \times 10^{-4}$, in a paramagnetic state above $T_c$, which is comparable to the spin susceptibility. The results suggest that orbitally induced Peierls transition in the proximity of the frustrated itinerant state is the dominant driving force of the trimerization transition.