Long-term relaxation of orientational disorder and structural modifications in molecular nitrogen at high pressure

Up to 17 GPa, the crystalline phases of N2 are characterized by pronounced orientational disorder, whereas the higher-pressure phases of molecular N2 are ordered. This raises the question about long-term relaxation of orientational disorder within the low- to intermediate-pressure regime. Here, this question is addressed by comparing synthetic with natural, chemically pure, solid N2 that resides as inclusions in diamonds at 300 K for about 108 years at pressures up to 11 GPa. It is shown that disorder prevails at 8.7 GPa, 300 K, where both synthetic and natural N2 assume the same structure. However, at 10.8 GPa, natural solid N2 exhibits monoclinic distortion and partial orientational ordering of the molecules, both of which are not observed in synthetic material. This difference is interpreted as the result of long-term structural relaxation. The ordering mechanism is examined and placed into the context of the δ- to ε-N2 transition. We present explanations for the absence of complete ordering of δ-N2.