Vibrational relaxation and small ’’bubble’’ spectroscopy of the NO 3sσ (A 2Σ+) Rydberg state in solid rare gases

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Abstract
The 1933 Å ArF excimer laser has been used to excite NO 3sσ Rydberg fluorescence in solid rare gases. A comparison of Rydberg and valence spectra indicates that Rydberg fluorescence is particularly sensitive to the nature of the local environment. The data demonstrate the limits of a continuum host approximation in the small ’’bubble’’ model. All observed emission is vibrationally relaxed. The relaxation rates appear to be many orders of magnitude faster than observed for ground state diatomics with equivalent vibrational quanta.