Transformation pathways in high-pressure solid nitrogen: from molecular N$_2$ to polymeric cg-N

Abstract

The transformation pathway in high-pressure solid nitrogen from N$_2$ molecular state to polymeric cg-N phase was investigated by means of \textit{ab initio} molecular dynamics and metadynamics simulations. In our study, we observed a transformation mechanism starting from molecular $Immm$ phase that initiated with formation of $trans$-$cis$ chains. These chains further connected within layers and formed a chain-planar state, which we describe as a mixture of two crystalline structures - $trans$-$cis$ chain phase and $planar$ phase, both with $Pnma$ symmetry. This mixed state appeared in molecular dynamics performed at 120 GPa and 1500 K and in the metadynamics run at 110 GPa and 1500 K, where the chains continued to reorganize further and eventually formed cg-N. During separate simulations, we also found two new phases - molecular $P2_1/c$ and two-three-coordinated chain-like $Cm$. The transformation mechanism heading towards cg-N can be characterized as a progressive polymerization process passing through several intermediate states of variously connected $trans$-$cis$ chains. In the final stage of the transformation chains in the layered form rearrange collectively and develop new intraplanar as well as interplanar bonds leading to the geometry of cg-N. Chains with alternating $trans$ and $cis$ conformation were found to be the key entity - structural pattern governing the dynamics of the simulated molecular-polymeric transformation in compressed nitrogen.