RESUMEN
In this Letter, the counterintuitive and largely unknown Raman activity of oxygen atoms is evaluated for its capacity to determine absolute densities in gases with significant O-density. The study involves ${\rm CO}_2$ microwave plasma to generate a self-calibrating mixture and establish accurate cross sections for the $^3{\!P_2}{\leftrightarrow ^3}{\!P_1}$ and $^3{\!P_2}{\leftrightarrow ^3}{\!P_0}$ transitions. The approach requires conservation of stoichiometry, confirmed within experimental uncertainty by a 1D fluid model. The measurements yield ${\sigma _{J = 2 \to 1}} = 5.27 \pm _{{\rm sys}:0.53}^{{\rm rand}:0.17} \times {10^{- 31}}\;{{\rm cm}^2}/{\rm sr}$ and ${\sigma _{J = 2 \to 0}} = 2.11 \pm _{{\rm sys}:0.21}^{{\rm rand}:0.06} \times {10^{- 31}}\;{{\rm cm}^2}/{\rm sr}$, and the detection limit is estimated to be $1 \times {10^{15}}\;{{\rm cm}^{- 3}}$ for systems without other scattering species.
RESUMEN
The contribution of higher vibrational levels to the rotational spectrum of linear polyatomic molecules with a center of symmetry (CO2 and C2H2) is assessed. An apparent nuclear degeneracy is analytically formulated by vibrational averaging and compared to numerical averaging over vibrational levels. It enables inferring the vibrational temperature of the bending and asymmetric stretching modes from the ratio of even to odd peaks in the rotational Raman spectrum. The contribution from higher vibrational levels is already observable at room temperature as gËe/o=0.96/0.04 for CO2 and gËe/o=1.16/2.84 for C2H2. The use of the apparent degeneracy to account for higher vibrational levels is demonstrated on spectra measured for a CO2 microwave plasma in the temperature range of 300-3500 K, and shown to be valid up to 1500 K.
RESUMEN
The strong non-equilibrium conditions provided by the plasma phase offer the opportunity to beat traditional thermal process energy efficiencies via preferential excitation of molecular vibrations. Simple molecular physics considerations are presented to explain potential dissociation pathways in plasma and their effect on energy efficiency. A common microwave reactor approach is evaluated experimentally with Rayleigh scattering and Fourier transform infrared spectroscopy to assess gas temperatures (exceeding 10(4) K) and conversion degrees (up to 30%), respectively. The results are interpreted on a basis of estimates of the plasma dynamics obtained with electron energy distribution functions calculated with a Boltzmann solver. It indicates that the intrinsic electron energies are higher than is favorable for preferential vibrational excitation due to dissociative excitation, which causes thermodynamic equilibrium chemistry to dominate. The highest observed energy efficiencies of 45% indicate that non-equilibrium dynamics had been at play. A novel approach involving additives of low ionization potential to tailor the electron energies to the vibrational excitation regime is proposed.