Two New Molecular Nitrogen Phases near Megabar Pressures

Abstract

Molecular nitrogen exhibits remarkable structural diversity near the polymeric transition, where multiple phases are metastable. Here, we report two new molecular phases. The first, $t\zeta$-N$_2$, is a polytype of monoclinic $C2/c$ $\zeta$-N$_2$, characterized by a tripled $c$ axis and 96 atoms per unit cell. The second, $\xi$-N$_2$, is a previously unreported hexagonal phase ($P6cc$) containing 112 atoms per unit cell. Both phases were synthesized in a diamond anvil cell by laser heating $\zeta$-N$_2$ to 1800--2500~K at pressures of 78--98~GPa. Their crystal structures were determined using single-crystal X-ray diffraction, corroborated by Raman spectroscopy, and supported by first-principles calculations. The $t\zeta$-N$_2$ phase likely corresponds to the previously reported $\kappa$-N$_2$ phase.