Effect of methyl rotation on the electronic spectrum of the methyl peroxy radical.
Recent experiments have prompted a theoretical investigation of the effect of methyl rotation on the A-X electronic spectrum of the CH3O2 and CD3O2 radicals. Quantum chemistry calculations have mapped the potential for the methyl rotation. Using these results, we calculate the torsional eigenvalues for both the A and X states and simulate the A-X spectrum. We find that the simulation captures the salient features of the spectrum. These features include torsional sequence structure, whose band contours change dramatically as the lower level nears the barrier, as well as atypical torsional transitions occurring from levels near the top and above the barrier. "Experimental" barrier heights are deduced for both the X and A states of methyl peroxy by modestly scaling the calculated potential to best reproduce the observed spectra.
Department of Chemistry, The Ohio State University, 120 West 18th Avenue, Columbus, Ohio 43210, USA.
Gabriel M P
GM
Just
Anne B
AB
McCoy
Terry A
TA
Miller