Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations

2017 
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 Koppel-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 e1/2 and e3/2 components of the 61 and 51 vibronic levels. A pair of spin-vibronic levels at 1638 and 1677 cm−...
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