Abstract
High-resolution anion photoelectron spectra of cryogenically cooled NO3̅ anions obtained using slow photoelectron velocity-map imaging are presented and provide new insight into the vibronic structure of the corresponding neutral radical. A combination of improved spectral resolution, measurement of energy-dependent intensity effects, temperature control, and comparison to theory allows for full assignment of the vibronic features observed in this spectrum. We obtain a refined electron affinity of 3.9289(14) eV for NO3. Further, the appearance of Franck-Condon forbidden transitions from vibrationally cold anions to neutral states with excitation along the NO3 ν4 mode confirms that these features arise from vibronic coupling with the B̃2E' excited state of NO3 and are not hot bands, as has been suggested. Together, the suite of experimental and simulated results provides clear evidence that the ν3 fundamental of NO3 resides near 1050 cm-1, addressing a long-standing controversy surrounding this vibrational assignment.
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