New insights into the Jahn – Teller effect in NO 3 via the dark à 2 E ′ ′ state
نویسندگان
چکیده
The recent cavity ringdown (CRD) measurement of the forbidden à 2E ← X̃ A2 transition of the nitrate radical NO3 reveals a rich, well-resolved spectrum in the near-infrared. The spectroscopic detail provides a new window onto the Jahn–Teller (JT) and pseudo-Jahn–Teller (PJT) effects in NO3. This paper reviews the current experimental evidence for vibronic coupling in the à state and discusses the theoretical issues in the context of new preliminary EOMIP/CCSD and CCSD(T) calculations. The theoretical results to date indicate that the à 2E ′′ state of NO3 undergoes a relatively strong JT distortion which may require inclusion of higher order vibronic couplings. The intensity of this transition may involve multiple intensity borrowing mechanisms via PJT coupling among the X̃ , à and B̃ states. PACS numbers: 31.10.+z, 31.25.Qm, 31.50.Df, 31.50.Gh, 33.20.Ea, 33.20.Wr
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