Cis-Trans Isomerization of Methyl Nitrite.

摘要

Intromolecular vibrational energy redistribution and intramolecular cis-trans and trans-cis conversions have been investigated as a function of initial excitation of C-H local stretch modes and some bending normal modes in methyl nitrite by using quasiclassical trajectories. Harmonic and anharmonic valence force-field potential-energy surfaces with parameter values based on the available experimental and ab initio results were used in the calculations. The anharmonic potential gives rates of energy transfer and isomerization that are significantly faster than those for the harmonic potential. The rate of cis-trans isomerization is significantly larger that the rate of trans-cis. The energy flow out of excited C-H local stretch modes is irreversible and essentially complete in less than 0.5 ps. Keywords: Reprints. (AW)