Fourier transform infrared study of the pressure and laser induced polymerization of solid acetylene

Abstract

The polymerization of solid acetylene under pressure has been studied by Fourier transform infrared (FTIR) spectroscopy. Controlled laser irradiation cycles and the employment of infrared sensors to measure the sample pressure, allowed to separate the photochemical and the pressure effect on the injection and on the evolution of the reaction. The careful assignment of all the spectral features and analysis of their relative intensities and frequencies gave evidence to the specific effect of pressure and laser irradiation on the reaction products. Pressure induces an ordered growth of trans-polyenic species, while irradiation produces the opening of the double bonds and a consequent branching of the chains. Constant pressure measurements allowed to obtain precise information on the kinetics of the reaction. A monodimensional growth geometry, involving the molecules on the bc plane, agrees with the parameters extracted by the kinetic curves. Comparison between experiments at different temperatures suggests an activation of the reaction essentially due to the translational lattice modes.