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  1. 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-SEVImore » 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 e1/2 and e3/2 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 e1/2 and e3/2 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. In conclusion, 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.« less

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