Time evolution of CO$_2$ ro-vibrational excitation in a nanosecond discharge measured with quantum cascade laser absorption spectroscopy

TL;DR

This study uses quantum cascade laser absorption spectroscopy to monitor the time evolution of CO₂ ro-vibrational excitation in nanosecond discharges, revealing non-thermal features, mode-specific excitation, and acoustic oscillations with high temporal resolution.

Contribution

It demonstrates a novel application of CW quantum cascade laser spectroscopy to track CO₂ excitation dynamics in non-equilibrium nanosecond discharges with microsecond resolution.

Findings

Observed non-thermal excitation features of CO₂ modes.

Measured decay times consistent with vibrational transfer mechanisms.

Detected acoustic oscillations linked to the discharge process.

Abstract

CO$_2$ dissociation stimulated by vibrational excitation in non-equilibrium discharges has drawn lots of attention. Ns-discharges are known for their highly non-equilibrium conditions. It is therefore of interest to investigate the CO$_2$ excitation in such discharges. In this paper, we demonstrate the ability for monitoring the time evolution of CO$_2$ ro-vibrational excitation with a well-selected wavelength window around 2289.0 cm$^{-1}$ and a single CW quantum cascade laser (QCL) with both high accuracy and temporal resolution. The rotational and vibrational temperatures for both the symmetric and the asymmetric modes of CO$_2$ in the afterglow of CO$_2$ + He ns-discharge were measured with a temporal resolution of 1.5 $\mu$s. The non-thermal feature and the preferential excitation of the asymmetric stretch mode of CO$_2$ were experimentally observed, with a peak temperature of $T_{v3, max}$ = 966 $\pm$ 1.5 K, $T_{v12, max}$ = 438.4 $\pm$ 1.2 K and $T_{rot}$ = 334.6 $\pm$ 0.6 K reached at 3 $\mu$s after the nanosecond pulse. In the following relaxation process, an exponential decay with a time constant of 69 $\mu$s was observed for the asymmetric stretch (001) state, consistent with the dominant deexcitation mechanism due to VT transfer with He and deexcitation on the wall. Furthermore, a synchronous oscillation of the gas temperature and the total pressure was also observed and can be explained by a two-line thermometry and adiabatic process. The period of the oscillation and its dependence on the gas components is consistent with a standing acoustic wave excited by the ns-discharge.