Matrix isolation study of the vacuum-ultraviolet photolysis of methanol: The infrared spectrum of the CH2OH free radical

Infrared studies of the products of the 1470 Å photolysis of normal and isotopically substituted methanol isolated in argon and nitrogen matrices at 14°K have provided evidence for the stabilization of a significant yield of CH₂OH. Assuming a slightly nonplanar structure for the molecule, it has been possible to obtain an approximate valence-force potential field which provides a reasonable fit to virtually all of the data. The CO bond of CH₂OH is slightly stronger than that of methanol, and the torsional barrier is significantly greater, in accord with previous electron spin resonance observations. There is no evidence for the production or stabilization of CH₃O in the matrix. CH₂OH undergoes photodecomposition upon exposure to radiation in the 2300–2800 Å spectral region, leading to a growth in the HCO absorptions.