Journal of Physical Chemistry A, Vol.102, No.1, 138-145, 1998
Magnetic circular dichroism of the CH radical in an argon matrix
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 (2) Delta <-- X (2) Pi, B (2) Sigma(-) <-- X (2) Pi, and C (2) Sigma(+) <-- X (2) Pi 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 A(Pi) = 21 +/- cm(-1) and orbital reduction factor kappa = 0.26 +/- 0.03, corresponding to a crystal-field splitting of V-Pi = 78 +/- 14 cm(-1) for the X (2) Pi term. For the A (2) Delta excited-state term, the first MCD moments give A(Delta) = 5 +/- 1 cm(-1), and an upper limit of V-Delta less than or similar to 15 cm(-1) is estimated from the dispersion of the MCD.