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1. One-dimensional temperature measurement of supersonic jet flow by resonantly ionized photoemission thermometry of molecular nitrogen

   https://doi.org/10.1364/OPTCON.543309  

   Clark, Aleksander; McCord, Walker; Pride, Kyle; Zhang, Zhili (December 2024, Optics Continuum)

   As the field of fluid dynamics progresses, the demand for sophisticated diagnostic methods to accurately assess flow conditions rises. In this work, resonantly ionized photoemission thermometry (RIPT) has been used to directly target and ionize diatomic nitrogen (N₂) to measure one-dimensional (1D) temperature profiles in a supersonic jet flow. This technique can be considered non-intrusive as the premise uses resonantly enhanced multiphoton ionization (REMPI) to target molecular nitrogen. This resonance excites N₂into absorption bands of the P, Q, and R rotational branches of N₂(b¹Π_u). The ideal (3 + 1) REMPI scheme excites from the ground state and ionizes N₂(b¹Π_u←X¹Σ_g⁺) where de-excitation results in photoemission from the first negative band of ionizedN₂⁺(B²Σ_u⁺→X²Σ_g⁺) as nitrogen returns to the ground state. The resulting emission can be observed using an intensified camera, thus permitting inference of the rotational temperature of ground-state molecular nitrogen. A linearly regressive Boltzmann distribution is applied based on previous calibration data for this technique to quantify the temperature along the ionized line. This work applies this technique to a pure N₂supersonic jet in cross-flow and counter-flow orientations to demonstrate N₂RIPT’s applications in a supersonic flow. Temperature variations are observed at different locations downstream of the exit in cross-flow, and axisymmetric in counter-flow, to generate profiles characterizing the flow dynamics. Due to the collisional effects resulting from the number density of N₂at higher pressures, a (3 + 2) REMPI scheme is observed throughout this text. 

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2. 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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3. 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 $N_2^{+}\left(B^2{\mathrm{\Sigma <\#comment/>}}_u^{+}-<\#comment/>X^2{\mathrm{\Sigma <\#comment/>}}_g^{+}\right)$. 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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4. H ₃ ⁺ absorption and emission in local (U)LIRGs with JWST/NIRSpec: Evidence for high H ₂ ionization rates

   https://doi.org/10.1051/0004-6361/202451741  

   Pereira-Santaella, Miguel; González-Alfonso, Eduardo; García-Bernete, Ismael; Donnan, Fergus R; Santa-Maria, Miriam G; Goicoechea, Javier R; Lamperti, Isabella; Perna, Michele; Rigopoulou, Dimitra (September 2024, Astronomy & Astrophysics)

   We study the 3.4 − 4.4 μm fundamental rovibrational band of H₃⁺, a key tracer of the ionization of the molecular interstellar medium (ISM), in a sample of 12 local (d < 400 Mpc) (ultra)luminous infrared galaxies ((U)LIRGs) observed with JWST/NIRSpec. TheP,Q, andRbranches of the band are detected in 13 out of 20 analyzed regions within these (U)LIRGs, which increases the number of extragalactic H₃⁺detections by a factor of 6. For the first time in the ISM, the H₃⁺band is observed in emission; we detect this emission in three regions. In the remaining ten regions, the band is seen in absorption. The absorptions are produced toward the 3.4 − 4.4 μm hot dust continuum rather than toward the stellar continuum, indicating that they likely originate in clouds associated with the dust continuum source. The H₃⁺band is undetected in Seyfert-like (U)LIRGs where the mildly obscured X-ray radiation from the active galactic nuclei might limit the abundance of this molecule. For the detections, the H₃⁺abundances,N(H₃⁺)/N_H = (0.5 − 5.5)×10⁻⁷, imply relatively high ionization rates,ζ_H2, of between 3 × 10⁻¹⁶and > 4 × 10⁻¹⁵s⁻¹, which are likely associated with high-energy cosmic rays. In half of the targets, the absorptions are blueshifted by 50–180 km s⁻¹, which is lower than the molecular outflow velocities measured using other tracers such as OH 119 μm or rotational CO lines. This suggests that H₃⁺traces gas close to the outflow-launching sites before it has been fully accelerated. We used nonlocal thermodynamic equilibrium models to investigate the physical conditions of these clouds. In seven out of ten objects, the H₃⁺excitation is consistent with inelastic collisions with H₂in warm translucent molecular clouds (T_kin ∼ 250–500 K andn(H₂) ∼10^2 − 3cm⁻³). In three objects, dominant infrared pumping excitation is required to explain the absorptions from the (3,0) and (2,1) levels of H₃⁺detected for the first time in the ISM. 

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5. 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)

   Abstract 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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