Characterization of the electronic properties of YB$_4$ and YB$_6$ using $^{11}$B NMR and first-principles calculations

TL;DR

This study combines $^{11}$B NMR measurements and first-principles calculations to characterize the electronic and structural properties of YB$_4$ and YB$_6$, revealing detailed insights into their electric-field gradients and bonding nature.

Contribution

It provides a comprehensive comparison of experimental NMR data with theoretical calculations, confirming structural models and elucidating electronic properties of YB$_4$ and YB$_6$.

Findings

EFG patterns differ between YB$_4$ and YB$_6$

Knight shifts are very small in both compounds

Theoretical results agree well with experimental data

Abstract

Two compounds, tetragonal YB$_4$ and cubic YB$_6$, have been investigated by electric-field gradient (EFG) and Knight shift measurements at the boron sites using the $^{11}$B nuclear magnetic resonance (NMR) technique and by performing first-principles calculations. In YB$_6$ $^{11}$B ($I=3/2$) NMR spectra reveal patterns typical for an axially symmetric field gradient with a quadrupole coupling frequency of $\nu_Q=600\pm15$ kHz. In the second boride (YB$_4$) three different EFGs were observed corresponding to the three inequivalent crystallographic sites for the boron atoms ($4h$, $4e$, and $8j$). They correspond to: $\nu_Q(4h)=700\pm30$ kHz with an asymmetry parameter $\eta=0.02\pm0.02$, $\nu_Q(4e)=515\pm30$ kHz, $\eta=0.00+0.02/-0.00$, and $\nu_Q(8j)=515\pm40$ kHz, $\eta=0.46\pm0.08$. The Knight shifts measured by Magic-Angle Spinning (MAS) NMR at room temperature are very small being $0.6\pm8$ ppm and $-1\pm8$ ppm for YB$_4$ and YB$_6$, respectively. For the theoretical calculations structure optimizations were performed as a first step. For the obtained structural parameters the EFGs were computed within the local-density approximation. Very satisfactory agreement between experimental and theoretical results is obtained both for the structural parameters and the B EFGs thus confirming the underlying structural models. In addition to the EFGs, band structures, densities of states, and valence-electron densities are presented and the bonding situation in the two yttrium borides is discussed. The band-structure results are compatible with the very low values for the Knight shifts mentioned above.