Sub-Doppler infrared spectroscopy of CH2OH radical in a slit supersonic jet: Vibration-rotation-tunneling dynamics in the symmetric CH stretch manifold.

The sub-Doppler CH-symmetric stretch (ν₃) infrared absorption spectrum of a hydroxymethyl (CH₂OH) radical is observed and analyzed with the radical formed in a slit-jet supersonic discharge expansion (T_rot = 18 K) via Cl atom mediated H atom abstraction from methanol. The high sensitivity of the spectrometer and reduced spectral congestion associated with the cooled expansion enable first infrared spectroscopic observation of hydroxymethyl transitions from both ± symmetry tunneling states resulting from large amplitude COH torsional motion. Nuclear spin statistics due to exchange of the two methyl H-atoms aid in unambiguous rovibrational assignment of two A-type K_a = 0 ← 0 and K_a = 1 ← 1 bands out of each ± tunneling state, with additional spectral information obtained from spin-rotation splittings in P, Q, and R branch K_a = 1 ← 1 transitions that become resolved at low N. A high level ab initio potential surface (CCSD(T)-f12b/cc-pvnzf12 (n = 2,3)/CBS) is calculated in the large amplitude COH torsional and CH₂ wag coordinates, which in the adiabatic approximation and with zero point correction predicts ground state tunneling splittings in good qualitative agreement with experiment. Of particular astrochemical interest, a combined fit of the present infrared ground state combination differences with recently reported millimeter-wave frequencies permits the determination of improved accuracy rotational constants for the ground vibrational state, which will facilitate ongoing millimeter/microwave searches for a hydroxymethyl radical in the interstellar medium. [ABSTRACT FROM AUTHOR]