Photolysis Within the Absorption Band Contour for Methyl Isocyanide: VibrationalOvertone Activation

摘要

The photoisomerization of methyl isocyanide to form acetonitrile induced byexcitation into the fourth (about 1 kcal/mole above the activation barrier) and fifth (about 8 kcal/mole 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, k(E), derived from Stern-Volmer plots with increasing excitation energies selected from across the rotational band contours, increase monotonically. The experimental k(E) agree with RRKM calculated values.