15min:

XIAOYONG LIU, VADIM STAKHURSKY, ERIC D. OLMON, VLADIMIR A. LOZOVSKY, TERRY A. MILLER, C. BRADLEY MOORE, The Ohio State University, Dept. of Chemistry, 120 W. 18th Avenue, Columbus, Ohio 43210, USA.

In the rotationally resolved LIF A X spectrum of the jet-cooled d₂-methoxy radical (CHD₂O), combination bands of C-O ( ₃) and C-H ( ₁) stretches 1¹3¹ and 1¹3² were assigned. Analysis of vibrationally resolved Dispersed Fluorescence (DF) and rotationally resolved Stimulated Emission Pumping (SEP) spectra recorded upon excitation of these bands reinforces LIF spectral assignments and gives C-H and C-O stretch along with pseudo-Jahn-Teller active d₂-methyl rock ( ₆'', ₆') vibrational frequencies in the X state. A splitting of about 200 cm^-1 for 1₁, 3₁1₁, 3₂1₁ vibronic levels of CHD₂O is observed and may be due to the combination of vibronic degeneracy lifting and unquenched spin-orbit interaction. The DF spectra of CH₃O were recorded for excitation of A²A₁ 3ⁿ4¹ (n=1,2,3) combination bands containing asymmetric ( ₄) stretch. X²E₁ 3₆4₁ and X²E₁ 3₇4₁ rovibronic levels which lie 500 cm^-1 and 1500 cm^-1, respectively, above the X²E CH₃O barrier for dissociation CH₂O + H products, exhibit splitting of 120 cm^-1.