Vibronic eigenstates and the geometric phase effect in the 2E″ state of NO3.

Abstract

The 2E″ state of NO3, a prototype for the Jahn-Teller effect, has been an enigma and a challenge for a long time for both experiment and theory. We present a detailed theoretical study of the vibronic quantum dynamics in this electronic state, uncovering the effects of tunnelling, geometric phase, and symmetry. To this end, 45 vibronic levels of NO3 in the 2E″ state are determined accurately and analyzed thoroughly. The computation is based on a high quality diabatic potential representation of the two-sheeted surface of the 2E″ state developed by us [W. Eisfeld et al., J. Chem. Phys. 140, 224109 (2014)] and on the multi-configuration time dependent Hartree approach. The vibrational eigenstates of the NO3- anion are determined and analyzed as well to gain a deeper understanding of the symmetry properties of such D3h symmetric systems. To this end, 61 eigenstates of the NO3- anion ground state are computed using the single sheeted potential surface of the 1A1 state published in the same reference quoted above. The assignments of both the vibrational and vibronic levels are discussed. A simple model is proposed to rationalize the computed NO3 spectrum strongly influenced by the Jahn-Teller couplings, the associated geometric phase effect, and the tunnelling. Comparison with the available spectroscopic data is also presented.