Excitation and relaxation of the asymmetric stretch mode of CO2 in a pulsed glow discharge

Abstract

The excitation and relaxation of the vibrations of CO2; as well as the reduction of CO2 to CO are studied in a pulsed glow discharge. Two diagnostics are employed, being (1) time-resolved in situ Fourier transform nfrared (FTIR) spectroscopy and (2) spatiotemporally resolved in situ rotational Raman spectroscopy. Experiments are conducted within a pressure range of 1.3-6.7 mbar and a current range of 10-50 mA. In the afterglow, the rate of exponential decay from the asymmetric stretch temperature (T3) to the rotational temperature (Trot) is found to be only dependent on Trot, in the conditions under study. The cay rate ρT3-Trot follows the relation ρT3-Trot = 388 s-1 exp(Trot - 273 K)/(154 K). Pressure and varying concentrations of CO and (presumably) atomic oxygen did not show to be of significant influence. In the active part of the discharge the excitation of T3 showed to be positively related to current and negatively to pressure. However, the contribution of current to vibrational excitation is ambiguous: the conversion of CO2 and therefore the fraction of CO in the discharge, is found to be strongly dependent on the current, with a conversion factor of 0.05 to 0.18 for 10 mA to 50 mA, while CO can contribute to the excitation through near-resonant collisions. A clear relation between the elevation of T3 and the dissociation of CO2 could not be confirmed, though conversion peaks are observed in the near afterglow, which motivate future experiments on vibrational ladder-climbing directly after termination of the discharge