Abstract
The v 3 = 1 ← 0 (out-of-phase stretching vibration) transition wavenumbers of gas-phase X ˜ 2 Π NCO have been measured, in many cases with sub-Doppler resolution, by mid-infrared laser magnetic resonance (LMR) spectroscopy. In addition to the fundamental transition from the 2Π ground vibronic state, hot bands from the v 2 = 1 2Σ and 2Δ and from the v 2 = 2 2Φ vibronic states were detected and analyzed. The 2Σ vibronic level, with a spin–orbit coupling only partly quenched by the Renner–Teller effect, is characterised by complex and rapid tuning of energies in the magnetic field. This is the first successful analysis of magnetic resonance spectra for non-unique Renner–Teller vibronic states. The new LMR transitions were combined with data from previous studies and analysed, using an effective Hamiltonian in a 40-parameter fit to 660 transitions and combination differences. Several new coupling parameters are required, having magnitudes generally consistent with predictions from standard vibration–rotation theory.
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