Electronic and vibrational relaxation in Rydberg and valence states of NO in Ne matrices

New time and energy resolved data on vibrationally relaxed and unrelaxed emissions from the valence a 4 Π(v=0), B 2 Π(v=0,3,4,5), and the Rydberg A 2 Σ+ (v=0,1,2) states of NO in Ne matrices are reported. Rydberg ↔ valence and valence ↔ valence nonradiative transitions are identified. The Rydberg → valence transitions are seen to occur after lattice relaxation accommodating the Rydberg orbital. The branching ratios for intramolecular relaxation and the measured lifetimes are described in terms of a model which combines the intramolecular spin–orbit matrix elements and Franck–Condon factors with the spectroscopically determined phonon Franck–Condon factors. For the levels B 2 Π(v=5,6), a Förster–Dexter‐type energy transfer between NO molecules is also invoked in the description of the relaxation cascade