Photo-and pressure-induced transformations in the linear orthorhombic polymer of C60

Abstract

Stability of the linear orthorhombic polymer of C60 under pressure and laser irradiation is studied by Raman scattering and X-ray diffraction measurements. The Raman spectrum at ambient pressure remains unchanged, in the time scale of the experiment, up to an intensity of 3200 W/cm2 of the 514.5 nm line of an Ar+ laser, but irreversible changes are observed at higher intensities. The Raman spectra recorded at increased pressure show similar irreversible changes even at the laser intensity as low as 470 W/cm2. The X-ray diffraction and Raman measurements of the pressure-treated samples, performed after pressure release, show that the nonirradiated material does not exhibit any changes in the crystal structure and phonon spectra. This behavior indicates a pressure-enhanced photo-induced transformation to a new polymeric phase characterized by a Raman spectrum that differs from those of the other known polymeric phases of C60. The Raman spectra of the phototransformed linear orthorhombic polymer of C60 were measured at a pressure of up to 29 GPa. The pressure dependence of the Raman mode frequencies show singularities near 4 GPa and 15 GPa, respectively, related to a reversible phase transition and an irreversible transformation to a metastable disordered phase. The diffuse Raman spectrum of the disordered phase does not exhibit substantial changes with an increase in pressure up to 29 GPa. The high-pressure phase transforms to a mixture of pristine and dimerized C60, after pressure release and exposure to ambient conditions for 30 h.