Electronic structure of single-crystalline Mg$_x$Al$_{1-x}$B$_2$ probed by x-ray diffraction multipole refinements and polarization-dependent x-ray absorption spectroscopy

TL;DR

This study investigates the electronic structure of Mg$_x$Al$_{1-x}$B$_2$ using x-ray techniques, revealing how hybridizations and electron distributions relate to superconductivity and bonding characteristics.

Contribution

It provides detailed insights into the anisotropic electronic structure and bonding nature of Mg$_x$Al$_{1-x}$B$_2$, highlighting differences between superconducting and non-superconducting compositions.

Findings

Superconducting MgB$_2$ shows rearranged boron hybridizations.

Mg is approximately divalent with ionic bonds in MgB$_2$.

AlB$_2$ exhibits significant covalent bonding with electron transfer to B sheets.

Abstract

X-ray diffraction multipole refinements of single-crystalline Mg$_x$Al$_{1-x}$B$_2$ and polarization-dependent near-edge x-ray absorption fine structure at the B 1$s$ edge reveal a strongly anisotropic electronic structure. Comparing the data for superconducting compounds ($x= 0.8$, 1.0) with those for the non-superconductor ($x=0$) gives direct evidence for a rearrangement of the hybridizations of the boron $p_z$ bonds and underline the importance of holes in the $\sigma$-bonded covalent $sp^2$ states for the superconducting properties of the diborides. The data indicate that Mg is approximately divalent in MgB$_2$ and suggest predominantly ionic bonds between the Mg ions and the two-dimensional B rings. For AlB$_2$ ($x=0$), on the other hand, about 1.5 electrons per Al atom are transferred to the B sheets while the residual 1.5 electrons remain at the Al site which suggests significant covalent bonding between the Al ions and the B sheets. This finding together with the static electron deformation density points to almost equivalent electron counts on B sheets of MgB$_2$ and AlB$_2$\@, yet with a completely different electron/hole distribution between the $\sigma$ and $\pi$ bonds.