Frenkel Line in Nitrogen Terminates at the Triple Point.

Abstract

Recent studies on supercritical nitrogen revealed clear changes in structural markers and dynamical properties when the coordination number approaches its maximum value. The line in P and T space where these changes occur is referred to as the Frenkel line. Here, we qualitatively reproduce such changes in the supercritical regime using the popular "optimized potential for liquid simulation" (OPLS) classical force field for molecular dynamics. Unfortunately, at 160 K, OPLS nitrogen predicts sublimation rather than producing a liquid phase; therefore, we developed our own force field to achieve quantitative agreement with experimental data. We confirm the asymptotic behavior of the coordination number on crossing the Frenkel line and note an associated change in the diffusion constant, consistent with the non-rigid to rigid liquid-like character of the "transition". The simulations allow us to track the Frenkel line to subcritical temperatures and demonstrate that it terminates at the triple point. This establishes the experimentally measurable changes, which could unequivocally determine the Frenkel line in other systems.