Emerging d−d orbital coupling between non-d-block main-group elements Mg and I at high pressure
Yan Liu, Tian Cui, Da Li
Abstract
d−d orbital coupling, which increases anisotropic and directional bonding, commonly occurs between d -block transition metals. Here, we report an unexpected d − d orbital coupling in the non- d -block main-group element compound Mg 2 I based on first-principles calculations. The unfilled d orbitals of Mg and I atoms under ambient conditions become part of the valence orbitals and couple with each other under high pressures, resulting in the formation of highly symmetric I−Mg−I covalent bonding in Mg 2 I, which forces the valence electrons of Mg atoms into the lattice voids to form interstitial quasi-atoms (ISQs). In turn, the ISQs highly interact with the crystal lattice, contributing to lattice stability. This study greatly enriches the fundamental understanding of chemical bonding between non- d -block main-group elements at high pressures.