Laser induced fluorescence spectroscopy of d2-methoxy radical and CH2DO high-resolution infrared spectroscopy of hydroxymethyl radical and formyl fluoride

The fluorescence excitation spectra (FLEX spectra) of the A 2A' ↔ X˜2E electronic transition of the CHD2O and CH2DO isotopomers of the methoxy radical are investigated. The reported spectra cover the range from the zero vibrational level of the A2A ' well (31614.9 cm-1) up to 4133 cm -1 of vibrational excitation for CHD2O, and from the zero vibrational level of the A2 A' well (31637.4 cm-1) up to 2300 cm-1 of vibrational excitation for CH 2DO. Seventy-six vibrational features are observed and assigned for CHD2O and twenty---for CH2DO; the positions of the assigned bands are fit to a Dunham expansion for both isotopomers.;The existing theory that describes the vibronic structure of the X˜2E ground state of CH 3O and the rotational structure of its individual X˜ 2E vibronic levels is extended to encompass the case of CHD2O and CH2DO.;The splitting within the lowest vibronic level of the X˜ 2E state of CHD2O (78 cm-1) and CH2DO (99 cm-1) is inferred from observation of the hot bands in the FLEX spectrum that originate from the second lowest spin-vibronic state.;The technique of fluorescence depletion spectroscopy (FDS) is utilized for investigation of the vibrational structure of HFCO and CH3O in the ground electronic states. The first and second overtones of HFCO, at 5841 and 8595 cm-1, respectively, are accessed and their spectra are taken with rotational resolution. The evidence of mixing of the second overtone vibrational state with two or more dark states is seen.;The spectrum of IR excitation of X˜2 E CH3O is taken in the range 4700 cm-1 to 5700 cm-1. The density of transition lines observed in the spectrum approaches within a factor of 0.84 the total density of vibronic levels of a given symmetry multiplied by the number of transitions allowed for each by the rotational selection rules. (Abstract shortened by UMI.).