Pressure-induced transitions in tetracyanoethylene: a Raman scattering study

We report the results of high-pressure Raman scattering studies of the cubic and monoclinic polymorphs of tetracyanoethylene (TCNE). The evolution of the Raman spectrum at high pressures suggests that the cubic form is stable up to about 8 GPa. Subsequent pressurization leads to a gradual loss of transparency, and the sample becomes opaque to visible light above 14 GPa. In the monoclinic samples, qualitative changes are observed in the Raman spectrum above 3.6 GPa which indicate a subtle phase transition around this pressure. These changes are reversible when the pressure is reduced from peak values of about 4.5 GPa. At still higher pressures, the sample progressively becomes black, similar to what is observed in cubic TCNE. The Raman spectrum of the sample above 7 GPa is indicative of polymerization of TCNE. The spectrum of the pressure cycled opaque phase shows broad features characteristic of an amorphous phase, which is understood as being due to random cross-linking of TCNE in the pressure-reducing cycle