Remarkable stability of \(\gamma\)-\(N_2\) and its prevalence in the nitrogen phase diagram

Solid nitrogen exhibits a panoply of phenomena ranging from complex molecular crystalline configurations to polymerization and closing band gap at higher densities. Among the elemental molecular solids, nitrogen stands apart for having phases, which can only be stabilized following particular pressure-temperature pathways, indicative of metastability and kinetic barriers. Here, through the combination of Raman spectroscopy and dynamic compression techniques, we find that the appearance of the whole nitrogen phase diagram is determined by the P-T paths taken below 2 GPa. We reveal the existence of the path- and phase-dependent triple point between the \(\beta\) $\beta$ - \(N_2\) $N_2$ , \(\delta _{loc}\) ${\delta }_{\mathit{loc}}$ - \(N_2\) $N_2$ and \(\gamma\) $\gamma$ - or \(\epsilon\) $ϵ$ - \(N_2\) $N_2$ . We further show that the \(\beta\) $\beta$ - \(N_2\) $N_2$ towards \(\gamma\) $\gamma$ - \(N_2\) $N_2$ path below the triple point, that evades \(\delta\) $\delta$ ( \(\delta _{loc}\) ${\delta }_{\mathit{loc}}$ )- \(N_2\) $N_2$ , results in the formation of \(\gamma\) $\gamma$ - \(N_2\) $N_2$ , which in turn becomes a dominant phase. We then demonstrate, that the \(\beta\) $\beta$ - \(N_2\) $N_2$ through \(\delta\) $\delta$ ( \(\delta _{loc}\) ${\delta }_{\mathit{loc}}$ )- \(N_2\) $N_2$ above the triple point path leads to the formation of \(\epsilon\) $ϵ$ - \(N_2\) $N_2$ and the “well-established” phase diagram. An additional pathway, which by-passes the rotationally inhibited modifications \(\delta\) $\delta$ ( \(\delta _{loc}\) ${\delta }_{\mathit{loc}}$ )- \(N_2\) $N_2$ , via rapid compression is found to produce \(\gamma\) $\gamma$ - \(N_2\) $N_2$ at higher temperatures. We argue that the pathway and phase sensitive triple point and the compression rate dependent phase formation challenge our understanding of this archetypal dense molecular solid.