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1. 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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2. Sub-Doppler infrared spectroscopy of resonance-stabilized hydrocarbon intermediates: ν ₃ / ν ₄ CH stretch modes and CH ₂ internal rotor dynamics of benzyl radical

   https://doi.org/10.1039/c7cp05776h  

   Kortyna, A.; Samin, A. J.; Miller, T. A.; Nesbitt, D. J. (January 2017, Physical Chemistry Chemical Physics)

   Highly reactive benzyl radicals are generated by electron dissociative attachment to benzyl chloride doped into a neon–hydrogen–helium discharge and immediately cooled to T rot = 15 K in a high density, supersonic slit expansion environment. The sub-Doppler spectra are fit to an asymmetric-top rotational Hamiltonian, thereby yielding spectroscopic constants for the ground ( v = 0) and first excited ( v = 1, ν 3 , ν 4 ) vibrational levels of the ground electronic state. The rotational constants obtained for the ground state are in good agreement with previous laser induced fluorescence measurements (LIF), with vibrational band origins ( ν 3 = 3073.2350 ± 0.0006 cm −1 , ν 4 = 3067.0576 ± 0.0006 cm −1 ) in agreement with anharmonically corrected density functional theory calculations. To assist in detection of benzyl radical in the interstellar medium, we have also significantly improved the precision of the ground state rotational constants through combined analysis of the ground state IR and LIF combination differences. Of dynamical interest, there is no evidence in the sub-Doppler spectra for tunneling splittings due to internal rotation of the CH 2 methylene subunit, which implies a significant rotational barrier consistent with partial double bond character in the CC bond. This is further confirmed with high level ab initio calculations at the CCSD(T)-f12b/ccpVdZ-f12 level, which predict a zero-point energy corrected barrier to internal rotation of Δ E tun ≈ 11.45 kcal mol −1 or 4005 cm −1 . In summary, the high-resolution infrared spectra are in excellent agreement with simple physical organic chemistry pictures of a strongly resonance-stabilized benzyl radical with a nearly rigid planar structure due to electron delocalization around the aromatic ring. 

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3. [La(η ^x -B _x )La] ⁻ ( x = 7–9): a new class of inverse sandwich complexes

   https://doi.org/10.1039/c8sc05443f  

   Chen, Teng-Teng; Li, Wan-Lu; Li, Jun; Wang, Lai-Sheng (February 2019, Chemical Science)

   Despite the importance of bulk lanthanide borides, nanoclusters of lanthanide and boron have rarely been investigated. Here we show that lanthanide–boron binary clusters, La 2 B x − , can form a new class of inverse-sandwich complexes, [Ln(η x -B x )Ln] − ( x = 7–9). Joint experimental and theoretical studies reveal that the monocyclic B x rings in the inverse sandwiches display similar bonding, consisting of three delocalized σ and three delocalized π bonds. Such monocyclic boron rings do not exist for bare boron clusters, but they are stabilized by the sandwiching lanthanide atoms. An electron counting rule is proposed to predict the sizes of the B x ring that can form stable inverse sandwiches. A unique (d-p)δ bond is found to play important roles in the stability of all three inverse-sandwich complexes. 

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4. Characterizing the origin band spectrum of isoquinoline with resonance enhanced multiphoton ionization and electronic structure calculations

   https://doi.org/10.1063/5.0168421  

   Krogmeier, Timothy J.; Pappas, Emerson S.; Reardon, Kylie A.; Rivera, Marcos R.; Head-Marsden, Kade; Parsons, Bradley F.; Schlimgen, Anthony W. (October 2023, The Journal of Chemical Physics)

   We report the experimental resonance enhanced multiphoton ionization spectrum of isoquinoline between 315 and 310 nm, along with correlated electronic structure calculations on the ground and excited states of this species. This spectral region spans the origin transitions to a π–π* excited state, which previous work has suggested to be vibronically coupled with a lower lying singlet n–π* state. Our computational results corroborate previous density functional theory calculations that predict the vertical excitation energy for the n–π* state to be higher than the π–π* state; however, we find an increase in the C–N–C angle brings the n–π* state below the energy of the π–π* state. The calculations find two out-of-plane vibrational modes of the n–π* state, which may be brought into near resonance with the π–π* state as the C–N–C bond angle increases. Therefore, the C–N–C bond angle may be important in activating vibronic coupling between the states. We fit the experimental rotational contour with a genetic algorithm to determine the excited state rotational constants and orientation of the transition dipole moment. The fits show a mostly in-plane polarized transition, and the projection of the transition dipole moment in the a-b plane is about 84° away from the a axis. These results are consistent with the prediction of our electronic structure calculations for the transition dipole moment of the π–π* excited state. 

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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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