A joint experimental and theoretical study is reported on the low-lying vibronic level structure of the ground state of the methoxy radical using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled, mass-selected anions (cryo-SEVI) and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations. The KDC vibronic model Hamiltonian in the present study was parametrized using high-level quantum chemistry, allowing the assignment of the cryo-SEVI spectra for vibronic levels of CH₃O up to 2000 cm^-1 and of CD₃O up to 1500 cm^-1 above the vibrational origin, using calculated vibronic wave functions. The adiabatic electron affinities of CH₃O and CD₃O are determined from the cryo-SEVI spectra to be 1.5689 ± 0.0007 eV and 1.5548 ± 0.0007 eV, respectively, demonstrating improved precision compared to previous work. Experimental peak splittings of <10 cm^-1 are resolved between the e_1/2 and e_3/2 components of the 6₁ and 5₁ vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm^-1 were predicted in the calculation as the e_1/2 and e_3/2 components of 6₂ levels and experimentally resolved for the first time. The strong variation of the spin-orbit splittings with a vibrational quantum number is in excellent agreement between theory and experiment. The observation of signals from nominally forbidden a₁ vibronic levels in the cryo-SEVI spectra also provides direct evidence of vibronic coupling between ground and electronically excited states of methoxy.

High-resolution anion photoelectron spectra of cryogenically cooled NiO₂^- anions, obtained using slow photoelectron velocity-map imaging (cryo-SEVI), are presented in tandem with coupled cluster electronic structure calculations including relativistic effects. The experimental spectra encompass the X̃¹Σ_g⁺ ← X̃²Π_g, ã³Π_g ← X̃²Π_g, and ùΠ_g ← X̃²Π_g photodetachment transitions of linear ONiO^0/-, revealing previously unobserved vibrational structure in all three electronic bands. The high-resolution afforded by cryo-SEVI allows for the extraction of vibrational frequencies for each state, consistent with those previously measured in the ground state and in good agreement with scalar-relativistic coupled-cluster calculations. Previously unobserved vibrational structure is observed in the ã³Π_g and ùΠ_g states and is tentatively assigned. Further, a refined electron affinity of 3.0464(7) eV for NiO₂ is obtained as well as precise term energies for the ã and à states of NiO₂ of 0.3982(7) and 0.7422(10) eV, respectively. Numerous Franck-Condon forbidden transitions involving the doubly degenerate ν₂ bending mode are observed and ascribed to Herzberg-Teller coupling to an excited electronic state.

Postnatal tissue quiescence is thought to be a default state in the absence of a proliferative stimulus such as injury. Although previous studies have demonstrated that certain embryonic developmental programs are reactivated aberrantly in adult organs to drive repair and regeneration, it is not well understood how quiescence is maintained in organs such as the lung, which displays a remarkably low level of cellular turnover. Here we demonstrate that quiescence in the adult lung is an actively maintained state and is regulated by hedgehog signalling. Epithelial-specific deletion of sonic hedgehog (Shh) during postnatal homeostasis in the murine lung results in a proliferative expansion of the adjacent lung mesenchyme. Hedgehog signalling is initially downregulated during the acute phase of epithelial injury as the mesenchyme proliferates in response, but returns to baseline during injury resolution as quiescence is restored. Activation of hedgehog during acute epithelial injury attenuates the proliferative expansion of the lung mesenchyme, whereas inactivation of hedgehog signalling prevents the restoration of quiescence during injury resolution. Finally, we show that hedgehog also regulates epithelial quiescence and regeneration in response to injury via a mesenchymal feedback mechanism. These results demonstrate that epithelial-mesenchymal interactions coordinated by hedgehog actively maintain postnatal tissue homeostasis, and deregulation of hedgehog during injury leads to aberrant repair and regeneration in the lung.