Abstract
Magnetic circular dichroism (MCD) and absorption spectra are reported for the CH (methylidyne or methyne) free radical isolated in an Ar matrix (CH/Ar) over the temperature range 1.4−15.9 K and the magnetic-field range 0−4 T. Data for the A 2Δ ← X 2Π, B 2Σ- ← X 2Π, and C 2Σ+ ← X 2Π band systems indicate a substantial quenching of the orbital angular momentum of the CH ground-state term. This is interpreted as being a consequence of crystal-field interactions involving atoms of the host lattice. Analysis of the zeroth moments of the spectra yields an empirical spin−orbit coupling constant AΠ = 21 ± 1 cm-1 and orbital reduction factor κ = 0.26 ± 0.03, corresponding to a crystal-field splitting of VΠ = 78 ± 14 cm-1 for the X 2Π term. For the A 2Δ excited-state term, the first MCD moments give AΔ = 5 ± 1 cm-1, and an upper limit of VΔ ≲ 15 cm-1 is estimated from the dispersion of the MCD.
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