Vibronic structure of the formyloxyl radical (HCO2) via slow photoelectron velocity-map imaging spectroscopy and model Hamiltonian calculations.

We report high-resolution photoelectron spectra of HCO(2)(-) and DCO(2)(-) obtained with slow photoelectron velocity-map imaging. Well-resolved photodetachment transitions to the (2)A(1) and (2)B(2) states of the neutral radicals were observed. In addition, vibronic levels of the HCO(2) and DCO(2) radicals with up to 2000 cm(-1) of internal energy were calculated using a quasidiabatic Hamiltonian approach and high-level ab initio calculations. Spectral simulations using the calculated levels were found to be in excellent agreement with the experimental spectra and used to assign many of its features. This study unambiguously determined that the (2)A(1) state is the ground state of both HCO(2) and DCO(2), in contrast to earlier work that indicated the (2)B(2) state was the ground state for DCO(2). For both isotopologs, the (2)B(2) state is a very low-lying excited state with term energies of T(0) = 318 +/- 8 cm(-1) for HCO(2) and T(0) = 87 +/- 8 cm(-1) for DCO(2). The adiabatic electron affinities are determined to be EA(HCO(2)) = 3.4961 +/- 0.0010 eV and EA(DCO(2)) = 3.5164 +/- 0.0010 eV.