Pure rotational coherent anti-Stokes Raman spectroscopy of ethylene, experiments and modelling

Abstract

Rotational coherent anti-Stokes Raman spectroscopy (CARS) is an established diagnostic technique for temperature and concentration measurements in combustion-related experiments. CARS has mainly been applied on di- and tri-atomics with linear molecular symmetry, for which good agreement is achieved between experimental and theoretical spectra. Hydrocarbons have so far been less attractive for rotational CARS studies, partly because of their complex molecular symmetries making it challenging to obtain molecular parameters necessary for a successful modeling. Nevertheless, in this work we have studied the asymmetric top molecule ethylene (C2H4) using rotational CARS through experiments and theoretical modelling. Experimental spectra have been recorded at temperatures between 293 K and 804 K, and theoretical spectra have been calculated with a novel method for which the crucial temperature-dependent linewidth parameters were determined by comparison of experimental and theoretically calculated spectra. Line-mixing effects and temperature dependence of the isolated linewidths were studied using a semi-classical approach considering an exponential gap law and a scaling law. Subsequently, theoretically calculated spectra were used to evaluate the temperatures of the experimental spectra for validation of the method. The evaluated temperatures were in good agreement with thermocouple temperatures with differences up to ±7 K. Hence, this work not only investigates the potential of using rotational CARS on ethylene for diagnostic purposes, but also expands the applicability of the technique to a whole new class of molecules with asymmetric-top molecular symmetry.