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1. Sensitive and single-shot OH and temperature measurements by femtosecond cavity-enhanced absorption spectroscopy

   https://doi.org/10.1364/OL.460338  

   Liu, Ning; Zhong, Hongtao; Chen, Timothy_Y; Lin, Ying; Wang, Ziyu; Ju, Yiguang (June 2022, Optics Letters)

   In many low-temperature plasmas (LTPs), the OH radical and temperature represent key properties of plasma reactivity. However, OH and temperature measurements in weakly ionized LTPs are challenging, due to the low concentration and short lifetime of OH and the abrupt temperature rise caused by fast gas heating. To address such issues, this Letter combined cavity-enhanced absorption spectroscopy (CEAS) with femtosecond (fs) pulses to enable sensitive single-shot broadband measurements of OH and temperature with a time resolution of ∼180 ns in LTPs. Such a combination leveraged several benefits. With the appropriately designed cavity, an absorption gain of ∼66 was achieved, enhancing the actual OH detection limit by ∼55× to the 10¹¹cm^-3level (sub-ppm in this work) compared with single-pass absorption. Single-shot measurements were enabled while maintaining a time resolution of ∼180 ns, sufficiently short for detecting OH with a lifetime of ∼100 μs. With the broadband fs laser, ∼34,000 cavity modes were matched with ∼95 modes matched on each CCD pixel bandwidth, such that fs-CEAS became immune to the laser-cavity coupling noise and highly robust across the entire spectral range. Also, the broadband fs laser allowed simultaneous sensing of many absorption features to enable simultaneous multi-parameter measurements with enhanced accuracies. 

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2. One dimensional temperature measurements by resonantly ionized photoemission thermometry of molecular nitrogen

   https://doi.org/10.1364/OPTCON.503546  

   McCord, Walker; Clarks, Aleksander; Zhang, Zhili (October 2023, Optics Continuum)

   This paper presents an extensive parameter study of a non-intrusive and non-seeded laser diagnostic method for measuring one dimensional (1D) rotational temperature of molecular nitrogen (N₂) at 165 - 450 K. Compared to previous efforts using molecular oxygen, here resonantly ionized and photoelectron induced fluorescence of molecular nitrogen for thermometry (N₂RIPT) was demonstrated. The RIPT signal is generated by directly probing various rotational levels within the rovibrational absorption band of N₂, corresponding to the 3-photon transition of N₂(X¹Σ_g⁺,v=0→b¹Π_u,v^′=6) near 285 nm, without involving collisional effects of molecular oxygen and nitrogen. The photoionized N₂produces strong first negative band of N₂⁺(B²Σ_u⁺−X²Σ_g⁺) near 390 nm, 420 nm, and 425 nm. Boltzmann analyses of various discrete fluorescence emission lines yield rotational temperatures of molecular nitrogen. By empirically choosing multiple rotational levels within the absorption band, non-scanning thermometry can be accurately achieved for molecular nitrogen. It is demonstrated that the N₂RIPT technique can measure 1D temperature profile up to ∼5 cm in length within a pure N₂environment. Multiple wavelengths are thoroughly analyzed and listed that are accurate for RIPT for various temperature ranges. 

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3. Laboratory Study of the Cameron Bands and UV Doublet in the Middle Ultraviolet 180–300 nm by Electron Impact upon CO ₂ with Application to Mars

   https://doi.org/10.3847/1538-4357/ac88c8  

   Lee, Rena A.; Ajello, Joseph M.; Malone, Charles P.; Evans, J. Scott; Veibell, Victoir; Holsclaw, Gregory M.; McClintock, William E.; Hoskins, Alan C.; Jain, Sonal K.; Gérard, Jean-Claude; et al (October 2022, The Astrophysical Journal)

   Abstract We have observed electron impact fluorescence from CO₂to excite the Cameron bands (CBs), CO (a³Π →X¹Σ⁺; 180–280 nm), the first-negative group (1NG) bands, CO⁺(B²Σ⁺→X²Σ⁺; 180–320 nm), the fourth-positive group (4PG) bands, CO (A¹Π →X¹Σ⁺; 111–280 nm), and the UV doublet, CO₂⁺( $\tilde{B}{}^2{\mathrm{\Sigma }}_u^{+}\to \tilde{X}{}^2{\mathrm{\Pi }}_g;$288.3 and 289.6 nm) in the ultraviolet (UV). This wavelength range matches the spectral region of past and present spacecraft equipped to observe UV dayglow and aurora emissions from the thermospheres (100–300 km) of Mars and Venus. Our large vacuum system apparatus is able to measure the emission cross sections of the strongest optically forbidden UV transitions found in planetary spectra. Based on our cross-sectional measurements, previous CB emission cross-sectional errors exceed a factor of 3. The UV doublet lifetime is perturbed through $\tilde{B}{}^2{\mathrm{\Sigma }}_u^{+}-\tilde{A}{}^2{\mathrm{\Pi }}_u$spin–orbit coupling. Forward modeling codes of the Mars dayglow have not been accurate in the mid-UV due to systematic errors in these two emission cross sections. We furnish absolute emission cross sections for several band systems over electron energies 20–100 eV for CO₂. We present a CB lifetime, which together with emission cross sections, furnish a set of fundamental physical constants for electron transport codes such as AURIC (Atmospheric Ultraviolet Radiance Integrated Code). AURIC and Trans-Mars are used in the analysis of UV spectra from the Martian dayglow and aurora. 

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4. The millimeter-wave spectrum of the SiP radical (X ² Π _i ): Rotational perturbations and hyperfine structure

   https://doi.org/10.1063/5.0118939  

   Burton, M. A.; Sheridan, P. M.; Ziurys, L. M. (November 2022, The Journal of Chemical Physics)

   The millimeter/submillimeter-wave spectrum of the SiP radical (X 2 Π i ) has been recorded using direct absorption spectroscopy in the frequency range of 151–532 GHz. SiP was synthesized in an AC discharge from the reaction of SiH 4 and gas-phase phosphorus, in argon carrier gas. Both spin–orbit ladders were observed. Fifteen rotational transitions were measured originating in the Ω = 3/2 ladder, and twelve in the Ω = 1/2 substate, each exhibiting lambda doubling and, at lower frequencies, hyperfine interactions from the phosphorus nuclear spin of I = 1/2. The lambda-doublets in the Ω = 1/2 levels appeared to be perturbed at higher J, with the f component deviating from the predicted pattern, likely due to interactions with the nearby excited A 2 Σ + electronic state, where ΔE Π-Σ ∼ 430 cm −1 . The data were analyzed using a Hund’s case a β Hamiltonian and rotational, spin–orbit, lambda-doubling, and hyperfine parameters were determined. A 2 Π/ 2 Σ deperturbation analysis was also performed, considering spin–orbit, spin-electronic, and L-uncoupling interactions. Although SiP is clearly not a hydride, the deperturbed parameters derived suggest that the pure precession hypothesis may be useful in assessing the 2 Π/ 2 Σ interaction. Interpretation of the Fermi contact term, b F , the spin-dipolar constant, c, and the nuclear spin-orbital parameter, a, indicates that the orbital of the unpaired electron is chiefly p π in character. The bond length in the v = 0 level was found to be r 0 = 2.076 Å, suggestive of a double bond between the silicon and phosphorus atoms. 

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5. Laboratory Study of the Cameron Bands, the First Negative Bands, and Fourth Positive Bands in the Middle Ultraviolet 180–280 nm by Electron Impact Upon CO

   https://doi.org/10.1029/2020JE006602  

   Lee, Rena A.; Ajello, Joseph M.; Malone, Charles P.; Evans, J. Scott; Veibell, Victoir; Holsclaw, Gregory M.; McClintock, William E.; Hoskins, Alan C.; Jain, Sonal; Gérard, Jean‐Claude; et al (January 2021, Journal of Geophysical Research: Planets)

   Abstract We have analyzed medium‐resolution (full width at half maximum, FWHM = 1.2 nm), Middle UltraViolet (MUV; 180–280 nm) laboratory emission spectra of carbon monoxide (CO) excited by electron impact at 15, 20, 40, 50, and 100 eV under single‐scattering conditions at 300 K. The MUV emission spectra at 100 eV contain the Cameron Bands (CB) CO(a³Π → X¹Σ⁺), the fourth positive group (4PG) CO(A¹Π → X¹Σ⁺), and the first negative group (1NG) CO⁺(B²Σ⁺→ X²Σ) from direct excitation and cascading‐induced emission of an optically thin CO gas. We have determined vibrational intensities and emission cross sections for these systems, important for modeling UV observations of the atmospheres of Mars and Venus. We have also measured the CB “glow” profile about the electron beam of the long‐lived CO (a³Π) state and determined its average metastable lifetime of 3 ± 1 ms. Optically allowed cascading from a host of triplet states has been found to be the dominant excitation process contributing to the CB emission cross section at 15 eV, most strongly by the d³Δ and a'³Σ⁺electronic states. We normalized the CB emission cross section at 15 eV electron impact energy by multilinear regression (MLR) analysis to the blended 15 eV MUV spectrum over the spectral range of 180–280 nm, based on the 4PG emission cross section at 15 eV that we have previously measured (Ajello et al., 2019,https://doi.org/10.1029/2018ja026308). We find the CB total emission cross section at 15 eV to be 7.7 × 10⁻¹⁷ cm². 

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