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1. One-dimensional air temperature measurements by air resonance enhanced multiphoton Ionization thermometry (ART)

   https://doi.org/10.1364/OE.455572  

   McCord, Walker ; Clark, Aleksander ; Zhang, Zhili ( May 2022 , Optics Express)

   In this work, a detailed calibration study is performed to establish non-intrusive one-dimensional (1D) rovibrational temperature measurements in unseeded air, based on air resonance enhanced multiphoton ionization thermometry (ART). ART is generated by REMPI (resonance enhanced multi-photon ionization) of molecular oxygen and subsequent avalanche ionization of molecular nitrogen in a single laser pulse. ART signal, the fluorescence from the first negative band of molecular nitrogen, is directly proportional to the 2-photon transition of molecular oxygen C³Π (v = 2) ← X³Σ (v’=0), which is used to determine temperature. Experimentally, hyperfine structures of the O₂rotational branches with high temperature sensitivity are selectively excited through a frequency-doubled dye laser. Electron-avalanche ionization of N₂results in the fluorescence emissions from the first negative bands of N₂⁺near 390, 425, and 430nm, which are captured as a 1D line by a gated intensified camera. Post processing of the N₂⁺fluorescence yields a 1D thermometry line that is representative of the air temperature. It is demonstrated that the technique provides ART fluorescence of ∼5cm in length in the unseeded air, presenting an attractive thermometry solution for high-speed wind tunnels and other ground test facilities.

    

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2. O 2 based resonantly ionized photoemission thermometry analysis of supersonic flows

   https://doi.org/10.1364/OE.471021  

   McCord, Walker ; Gragston, Mark ; Plemmons, David ; Zhang, Zhili ( October 2022 , Optics Express)

   Characterization of the thermal gradients within supersonic and hypersonic flows is essential for understanding transition, turbulence, and aerodynamic heating. Developments in novel, impactful non-intrusive techniques are key for enabling flow characterizations of sufficient detail that provide experimental validation datasets for computational simulations. In this work, Resonantly Ionized Photoemission Thermometry (RIPT) signals are directly imaged using an ICCD camera to realize the techniques 1D measurement capability for the first time. The direct imaging scheme presented for oxygen-based RIPT (O₂RIPT) uses the previously established calibration data to direct excite various resonant rotational peaks within the S-branch of theC³Π, (v = 2) ← X³Σ(v^′ = 0) absorption band of O₂. The efficient ionization of O₂liberates electrons that induce electron avalanche ionization of local N₂molecules generating N₂⁺, which primarily deexcites via photoemissions of the first negative band of$N_2^{+}(B^2{\mathrm{\Sigma <\#comment/>}}_u^{+}-<\#comment/>X^2{\mathrm{\Sigma <\#comment/>}}_g^{+})$. When sufficient lasing energy is used, the ionization region and subsequent photoemission signal is achieved along a 1D line thus, if directly imaged can allow for gas temperature assignments along said line; demonstrated here of up to five centimeters in length. The temperature gradients present within the ensuing shock train of a supersonic under expanded free jet serves as a basis of characterization for this new RIPT imaging scheme. The O₂RIPT results are extensively compared and validated against well-known and established techniques (i.e., CARS and CFD). The direct imaging capability fully realizes the technique’s fundamental potential and is expected to be the standard of implementation going forward. The direct imaging capability can play instrumental roles in future scientific studies that rely upon acute characterization of thermal gradients within a medium that cannot be easily resolved by a point. Furthermore, the removal of the spectrometer greatly reduces the cost, complexity, and optical alignment associated with prior RIPT measurements.

    

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3. Rotation‐Inversion Isomerization of Tertiary Carbamates: Potential Energy Surface Analysis of Multi‐Paths Isomerization Using Boltzmann Statistics

   https://doi.org/10.1002/cphc.202200442  

   Jameson, Brian ; Glaser, Rainer ( October 2022 , ChemPhysChem)

   Potential energy surface (PES) analyses at the SMD[MP2/6–311++G(d,p)] level and higher‐level energies up to MP4(fc,SDTQ) are reported for the fluorinated tertiary carbamateN‐ethyl‐N‐(2,2,2‐trifluoroethyl) methyl carbamate (VII) and its parent systemN,N‐dimethyl methyl carbamate (VI). Emphasis is placed on the analysis of the rotational barrier about the CN carbamate bond and its interplay with the hybridization of theN‐lone pair (NLP). All rotational transition state (TS) structures were found by computation of 1D relaxed rotational profiles but only 2D PES scans revealed the rotation‐inversion paths in a compelling fashion. We found four unique chiral minima ofVII, one pair each ofE‐andZ‐rotamers, and we determined theeightunique rotational TS structures associated with every possibleE/Z‐isomerization path. It is a significant finding that all TS structures featureN‐pyramidalization whereas the minima essentially contain sp²‐hybridized nitrogen. We will show that the TS stabilities are affected by the synergetic interplay between NLP/CO₂repulsion minimization, NLP→σ^*(CO) negative hyperconjugation, and two modes of intramolecular through‐space electrostatic stabilization. We demonstrate how Boltzmann statistics must be applied to determine the predicted experimental rotational barrier based on the energetics of all eight rotamerization pathways. The computed barrier forVIIis in complete agreement with the experimentally measured barrier of the very similar fluorinated carbamateN‐Boc‐N‐(2,2,2‐trifluoroethyl)‐4‐aminobutan‐1‐olII. NMR properties ofVIIwere calculated with a variety of density functional/basis set combinations and Boltzmann averaging over theE‐andZ‐rotamers at our best theoretical level results in good agreement with experimental chemical shifts δ(¹³C) andJ(¹³C,¹⁹F) coupling constants ofII(within 6 %).

    

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4. 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)

   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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5. A Surface Se‐Substituted LiCo[O 2− δ Se δ ] Cathode with Ultrastable High‐Voltage Cycling in Pouch Full‐Cells

   https://doi.org/10.1002/adma.202005182  

   Zhu, Zhi ; Wang, Hua ; Li, Yao ; Gao, Rui ; Xiao, Xianghui ; Yu, Qipeng ; Wang, Chao ; Waluyo, Iradwikanari ; Ding, Jiaxin ; Hunt, Adrian ; et al ( November 2020 , Advanced Materials)

   Cycling LiCoO₂to above 4.5 V for higher capacity is enticing; however, hybrid O anion‐ and Co cation‐redox (HACR) at high voltages facilitates intrinsic O^α−(α < 2) migration, causing oxygen loss, phase collapse, and electrolyte decomposition that severely degrade the battery cyclability. Hereby, commercial LiCoO₂particles are operando treated with selenium, a well‐known anti‐aging element to capture oxygen‐radicals in the human body, showing an “anti‐aging” effect in high‐voltage battery cycling and successfully stopping the escape of oxygen from LiCoO₂even when the cathode is cycled to 4.62 V. Ab initio calculation and soft X‐ray absorption spectroscopy analysis suggest that during deep charging, the precoated Se will initially substitute some mobile O^α−at the charged LiCoO₂surface, transplanting the pumped charges from O^α−and reducing it back to O²⁻to stabilize the oxygen lattice in prolonged cycling. As a result, the material retains 80% and 77% of its capacity after 450 and 550 cycles under 100 mA g⁻¹in 4.57 V pouch full‐cells matched with a graphite anode and an ultralean electrolyte (2 g Ah⁻¹).

    

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