Photolysis Within the Absorption Band Contour for Methyl Isocyanide: Vibrational Overtone Activation
BOWLING GREEN STATE UNIV OH CENTER FOR PHOTOCHEMICAL SCIENCES
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The photoisomerization of methyl isocyanide to form acetonitrile induced by excitation into the fourth about 1 kcalmole above the activation barrier and fifth about 8 kcalmole above the barrier C-H stretch vibrational overtone levels is reported. Four photolysis wavelengths within the 5-0 band contour and three within the 6-0 contour were selected. The specific rate constant, kE, derived from Stern-Volmer plots with increasing excitation energies selected from across the rotational band contours, increase monotonically. The experimental kE agree with RRKM calculated values.