On the vibronic level structure in the NO3 radical. I. The ground electronic state.

The model Hamiltonian approach of Köppel et al. [Adv. Chem. Phys. 57, 59 (1984)] is used to analyze the electronic spectroscopy of the nitrate radical (NO3). Simulations of negative ion photodetachment of NO3-, the X 2A2′←B 2E′ dispersed fluorescence spectrum of NO3, and the B 2E′←X 2A2′ absorption spectrum are all in qualitative agreement with experiment, indicating that the model Hamiltonian contains most or all of the essential physics that govern the strongly coupled X 2A2′ and B 2E′ electronic states of the radical. All 14 bands seen in the dispersed fluorescence spectrum below 2600 cm-1 are assigned based on the simulations, filling in a few gaps left by previous work, and 7 additional bands below 4000 cm-1 are tentatively assigned. The assignment is predicated on the assumption that the ν3 level of NO3 is near 1000 cm-1 rather than 1492 cm-1 as is presently believed. Support for this reassignment (which associates the 1492 cm-1 band with the ν1+ν4 level) comes from both the model Hamiltonian spectrum and a Fourier-transform infrared feature at 2585 cm-1 that is consistent with the large and positive cross anharmonicity between ν1 and ν4 needed for the alternative 1492 cm-1 assignment. An apparent systematic deficiency exists in the treatment of the model Hamiltonian for levels involving ν4. A discussion of the correlation between energy levels in the rigid D3h and C2v limits is illustrative, and provides insight into just how hard it is to treat the degenerate bending coordinate (q4) of NO3 accurately. [ABSTRACT FROM AUTHOR]