First-order liquid-liquid phase transition in nitrogen-oxygen mixtures

The first-order liquid-liquid phase transition (LLPT) describes the counterintuitive nature between two distinct liquids in a single system. However, the physical understanding of LLPT in simple liquid mixtures has remained elusive. Here, a first-order LLPT for nitrogen-oxygen (N-O) mixtures is investigated via extensive ab initio molecular dynamics simulations. The first-order LLPT is characterized by discontinuities of a short-range order and transport properties, occurring at the transition pressures identified by looking at isotherms. The LLPT in N-O mixtures is dominated primarily by the molecular-to-polymeric transformation. The resulting phase boundaries and further structural analysis show the crucial influence of oxygen on weakening the LLPT of N-O mixtures by promoting chemical reactions with nitrogen and crippling polymerizations. Furthermore, noncovalent interactions of short- to long-range van der Waals have evident impacts on the LLPT boundary. The introduction of the strongly constrained and appropriately normed functional with revised Vydrov--van Voorhis nonlocal correlation (SCAN-$r\mathrm{VV}10$) functional to describe the phase-transition behaviors improves the agreement with experimental data. The results highlight the characteristic features of the complex interplay in binary mixtures and revisit the first-order phase transition of dense nitrogen.