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1. The dicarbon bonding puzzle viewed with photoelectron imaging

   https://doi.org/10.1038/s41467-019-13039-y  

   Laws, B. A. ; Gibson, S. T. ; Lewis, B. R. ; Field, R. W. ( December 2019 , Nature Communications)

   null (Ed.)

   Abstract Bonding in the ground state of C $${}_{2}$$ 2 is still a matter of controversy, as reasonable arguments may be made for a dicarbon bond order of $$2$$ 2 , $$3$$ 3 , or $$4$$ 4 . Here we report on photoelectron spectra of the C $${}_{2}^{-}$$ 2 − anion, measured at a range of wavelengths using a high-resolution photoelectron imaging spectrometer, which reveal both the ground $${X}^{1}{\Sigma}_{\mathrm{g}}^{+}$$ X 1 Σ g + and first-excited $${a}^{3}{\Pi}_{{\mathrm{u}}}$$ a 3 Π u electronic states. These measurements yield electron angular anisotropies that identify the character of two orbitals: the diffuse detachment orbital of the anion and the highest occupied molecular orbital of the neutral. This work indicates that electron detachment occurs from predominantly $$s$$ s -like ( $$3{\sigma}_{\mathrm{g}}$$ 3 σ g ) and $$p$$ p -like ( $$1{\pi }_{{\mathrm{u}}}$$ 1 π u ) orbitals, respectively, which is inconsistent with the predictions required for the high bond-order models of strongly $$sp$$ s p -mixed orbitals. This result suggests that the dominant contribution to the dicarbon bonding involves a double-bonded configuration, with 2 $$\pi$$ π bonds and no accompanying $$\sigma$$ σ bond. 

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2. 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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3. 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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4. Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

   https://doi.org/10.1126/science.abd3054  

   Martinez, Jorge L. ; Lutz, Sean A. ; Yang, Hao ; Xie, Jiaze ; Telser, Joshua ; Hoffman, Brian M. ; Carta, Veronica ; Pink, Maren ; Losovyj, Yaroslav ; Smith, Jeremy M. ( October 2020 , Science)

   High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of2and3revealed four-coordinate Fe centers with an unusual “seesaw” geometry.⁵⁷Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S= 1/2) d³Fe(V) configuration in2and a diamagnetic (S= 0) d²Fe(VI) configuration in3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido σ- and π-bonding interactions.

    

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5. Dipole effects in the photoelectron angular distributions of the sulfur monoxide anion

   https://doi.org/10.1039/D2CP03337B  

   Ru, Beverly ; Hart, C. Annie ; Mabbs, Richard ; Gozem, Samer ; Krylov, Anna I. ; Sanov, Andrei ( October 2022 , Physical Chemistry Chemical Physics)

   Photoelectron angular distributions (PADs) in SO − photodetachment using linearly polarized 355 nm (3.49 eV), 532 nm (2.33 eV), and 611 nm (2.03 eV) light were investigated via photoelectron imaging spectroscopy. The measurements at 532 and 611 nm access the X 3 Σ − and a 1 Δ electronic states of SO, whereas the measurements at 355 nm also access the b 1 Σ + state. In aggregate, the photoelectron anisotropy parameter values follow the general trend with respect to electron kinetic energy (eKE) expected for π*-orbital photodetachment. The trend is similar to O 2 − , but the minimum of the SO − curve is shifted to smaller eKE. This shift is mainly attributed to the exit-channel interactions of the departing electron with the dipole moment of the neutral SO core, rather than the differing shapes of the SO − and O 2 − molecular orbitals. Of the several ab initio models considered, two approaches yield good agreement with the experiment: one representing the departing electron as a superposition of eigenfunctions of a point dipole-field Hamiltonian, and another describing the outgoing electron in terms of Coulomb waves originating from two separated charge centers, with a partial positive charge on the sulfur and an equal negative charge on the oxygen. These fundamentally related approaches support the conclusion that electron–dipole interactions in the exit channel of SO − photodetachment play an important role in shaping the PADs. While a similar conclusion was previously reached for photodetachment from σ orbitals of CN − (Hart, Lyle, Spellberg, Krylov, Mabbs, J. Phys. Chem. Lett. , 2021, 12 , 10086–10092), the present work includes the first extension of the dipole-field model to detachment from π* orbitals. 

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