Abstract
Magnetic circular dichroism (MCD) and absorption spectra are reported for the A 3Πi ← X 3Σ- transition of imidogen (NH) isolated in Kr, Xe, and N2 matrices at cryogenic temperatures (∼1.4−20 K) and over a range of magnetic field strengths (0−5 T). The results are analyzed by the method of moments, and parameters are extracted by fitting the experimental data to a model in which the A 3Πi term is split by spin−orbit (SO) coupling interactions and the X 3Σ- term is split by spin−spin and higher-order SO coupling. The analysis indicates that the ground-state NH radicals behave essentially as free rotors in the noble-gas matrices but as hindered rotors in solid N2. Trends in excited-state SO coupling constants are attributed to the external heavy-atom effect.
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