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1. Quantum electronic control on chemical activation of methane by collision with spin–orbit state selected vanadium cation

   https://doi.org/10.1039/D0CP04333H  

   Ng, Cheuk-Yiu; Xu, Yuntao; Chang, Yih-Chung; Wannenmacher, Anna; Parziale, Matthew; Armentrout, P. B. (January 2021, Physical Chemistry Chemical Physics)

   null (Ed.)

   By coupling a newly developed quantum-electronic-state-selected supersonically cooled vanadium cation (V + ) beam source with a double quadrupole-double octopole (DQDO) ion–molecule reaction apparatus, we have investigated detailed absolute integral cross sections ( σ 's) for the reactions, V + [a 5 D J ( J = 0, 2), a 5 F J ( J = 1, 2), and a 3 F J ( J = 2, 3)] + CH 4 , covering the center-of-mass collision energy range of E cm = 0.1–10.0 eV. Three product channels, VH + + CH 3 , VCH 2 + + H 2 , and VCH 3 + + H, are unambiguously identified based on E cm -threshold measurements. No J -dependences for the σ curves ( σ versus E cm plots) of individual electronic states are discernible, which may indicate that the spin–orbit coupling is weak and has little effect on chemical reactivity. For all three product channels, the maximum σ values for the triplet a 3 F J state [ σ (a 3 F J )] are found to be more than ten times larger than those for the quintet σ (a 5 D J ) and σ (a 5 F J ) states, showing that a reaction mechanism favoring the conservation of total electron spin. Without performing a detailed theoretical study, we have tentatively interpreted that a weak quintet-to-triplet spin crossing is operative for the activation reaction. The σ (a 5 D 0 , a 5 F 1 , and a 3 F 2) measurements for the VH + , VCH 2 + , and VCH 3 + product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH 4 have allowed the determination of the 0 K bond dissociation energies: D 0 (V + –H) = 2.02 (0.05) eV, D 0 (V + –CH 2 ) = 3.40 (0.07) eV, and D 0 (V + –CH 3 ) = 2.07 (0.09) eV. Detailed branching ratios of product ion channels for the titled reaction have also been reported. Excellent simulations of the σ curves obtained previously for V + generated by surface ionization at 1800–2200 K can be achieved by the linear combination of the σ (a 5 D J , a 5 F J , and a 3 F J ) curves weighted by the corresponding Boltzmann populations of the electronic states. In addition to serving as a strong validation of the thermal equilibrium assumption for the populations of the V + electronic states in the hot filament ionization source, the agreement between these results also confirmed that the V + (a 5 D J , a 5 F J , and a 3 F J ) states prepared in this experiment are in single spin–orbit states with 100% purity. 

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2. Thermochemistry and mechanisms of the Pt ⁺ + SO ₂ reaction from guided ion beam tandem mass spectrometry and theory

   https://doi.org/10.1063/5.0091510  

   Armentrout, P. B. (May 2022, The Journal of Chemical Physics)

   The kinetic energy dependences of the reactions of Pt + ( 2 D 5/2 ) with SO 2 were studied using a guided ion beam tandem mass spectrometer and theory. The observed cationic products are PtO + and PtSO + , with small amounts of PtS + , all formed in endothermic reactions. Modeling the kinetic energy dependent product cross sections allows determination of the product bond dissociation energies (BDEs): D 0 (Pt + –O) = 3.14 ± 0.11 eV, D 0 (Pt + –S) = 3.68 ± 0.31 eV, and D 0 (Pt + –SO) = 3.03 ± 0.12 eV. The oxide BDE agrees well with more precise literature values, whereas the latter two results are the first such measurements. Quantum mechanical calculations were performed for PtO + , PtS + , PtO 2 + , and PtSO + at the B3LYP and coupled-cluster with single, double, and perturbative triple [CCSD(T)] levels of theory using the def2-XZVPPD (X = T, Q) and aug-cc-pVXZ (X = T, Q, 5) basis sets and complete basis set extrapolations. These theoretical BDEs agree well with the experimental values. After including empirical spin–orbit corrections, the product ground states are determined as PtO + ( 4 Σ 3/2 ), PtS + ( 4 Σ 3/2 ), PtO 2 + ( 2 Σ g + ), and PtSO + ( 2 A′). Potential energy profiles including intermediates and transition states for each reaction were also calculated at the B3LYP/def2-TZVPPD level. Periodic trends in the thermochemistry of the group 9 metal chalcogenide cations are compared, and the formation of PtO + from the Pt + + SO 2 reaction is compared with those from the Pt + + O 2 , CO 2 , CO, and NO reactions. 

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3. Square-planar Co( iii ) in {O ₄ } coordination: large ZFS and reactivity with ROS

   https://doi.org/10.1039/c8cc04464c  

   Steele, Jennifer L.; Tahsini, Laleh; Sun, Chen; Elinburg, Jessica K.; Kotyk, Christopher M.; McNeely, James; Stoian, Sebastian A.; Dragulescu-Andrasi, Alina; Ozarowski, Andrew; Ozerov, M.; et al (October 2018, Chemical Communications)

   Oxidation of distorted square-planar perfluoropinacolate Co compound [Co II (pin F ) 2 ] 2− , 1 , to [Co III (pin F ) 2 ] 1− , 2 , is reported. Rigidly square-planar 2 has an intermediate-spin, S = 1, ground state and very large zero-field splitting (ZFS) with D = 67.2 cm −1 ; | E | = 18.0 cm −1 , ( E / D = 0.27), g ⊥ = 2.10, g ‖ = 2.25 and χ TIP = 1950 × 10 −6 cm 3 mol −1 . This Co( iii ) species, 2 , reacts with ROS to oxidise two (pin F ) 2− ligands to form tetrahedral [Co II (Hpfa) 4 ] 2− , 3 . 

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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. Marginal metallic state at a fractional filling of ’8/5’ and ’4/3’ of Landau levels in the GaAs/AlGaAs 2D electron system

   https://doi.org/10.1038/s41598-021-94563-0  

   Mani, R. G.; Wijewardena, U. K.; Nanayakkara, T. R.; Kriisa, Annika; Reichl, C.; Wegscheider, W. (December 2021, Scientific Reports)

   null (Ed.)

   Abstract A metallic state with a vanishing activation gap, at a filling factor $$\nu = 8/5$$ ν = 8 / 5 in the untilted specimen with $$n= 2 \times 10^{11} cm^{-2}$$ n = 2 × 10 11 c m - 2 , and at $$\nu = 4/3$$ ν = 4 / 3 at $$n=1.2 \times 10^{11} cm^{-2}$$ n = 1.2 × 10 11 c m - 2 under a $$\theta = 66^{0}$$ θ = 66 0 tilted magnetic field, is examined through a microwave photo-excited transport study of the GaAs/AlGaAs 2 dimensional electron system (2DES). The results presented here suggest, remarkably, that at the possible degeneracy point of states with different spin polarization, where the 8/5 or 4/3 FQHE vanish, there occurs a peculiar marginal metallic state that differs qualitatively from a quantum Hall insulating state and the usual quantum Hall metallic state. Such a marginal metallic state occurs most prominently at $$\nu =8/5$$ ν = 8 / 5 , and at $$\nu =4/3$$ ν = 4 / 3 under tilt as mentioned above, over the interval $$1 \le \nu \le 2$$ 1 ≤ ν ≤ 2 , that also includes the $$\nu = 3/2$$ ν = 3 / 2 state, which appears perceptibly gapped in the first instance. 

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