jats:titleAbstract</jats:title>jats:pSolid 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 jats:italicP-T</jats:italic> paths taken below 2 GPa. We reveal the existence of the path- and phase-dependent triple point between the jats:inline-formulajats:alternativesjats:tex-math$$\beta$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miβ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>, jats:inline-formulajats:alternativesjats:tex-math$$\delta _{loc}$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miδ</mml:mi> mml:mrow mml:miloc</mml:mi> </mml:mrow> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> and jats:inline-formulajats:alternativesjats:tex-math$$\gamma$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miγ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>- or jats:inline-formulajats:alternativesjats:tex-math$$\epsilon$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miϵ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>. We further show that the jats:inline-formulajats:alternativesjats:tex-math$$\beta$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miβ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> towards jats:inline-formulajats:alternativesjats:tex-math$$\gamma$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miγ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> path below the triple point, that evades jats:inline-formulajats:alternativesjats:tex-math$$\delta$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miδ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>(jats:inline-formulajats:alternativesjats:tex-math$$\delta _{loc}$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miδ</mml:mi> mml:mrow mml:miloc</mml:mi> </mml:mrow> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>)-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>, results in the formation of jats:inline-formulajats:alternativesjats:tex-math$$\gamma$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miγ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>, which in turn becomes a dominant phase. We then demonstrate, that the jats:inline-formulajats:alternativesjats:tex-math$$\beta$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miβ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> through jats:inline-formulajats:alternativesjats:tex-math$$\delta$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miδ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>(jats:inline-formulajats:alternativesjats:tex-math$$\delta _{loc}$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miδ</mml:mi> mml:mrow mml:miloc</mml:mi> </mml:mrow> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>)-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> above the triple point path leads to the formation of jats:inline-formulajats:alternativesjats:tex-math$$\epsilon$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miϵ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> and the “well-established” phase diagram. An additional pathway, which by-passes the rotationally inhibited modifications jats:inline-formulajats:alternativesjats:tex-math$$\delta$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miδ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>(jats:inline-formulajats:alternativesjats:tex-math$$\delta _{loc}$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miδ</mml:mi> mml:mrow mml:miloc</mml:mi> </mml:mrow> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>)-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>, via rapid compression is found to produce jats:inline-formulajats:alternativesjats:tex-math$$\gamma$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:miγ</mml:mi> </mml:math></jats:alternatives></jats:inline-formula>-jats:inline-formulajats:alternativesjats:tex-math$$N_2$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> mml:msub mml:miN</mml:mi> mml:mn2</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula> 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.</jats:p>