Ey. Davydov et al., EFFECT OF SPACE-ORIENTATION FACTORS ON KINETICS OF LOW-TEMPERATURE CARBENE REACTIONS, Journal of physical chemistry, 100(30), 1996, pp. 12403-12409
The character of nonexponential kinetics of the low-temperature decay
of triplet carbenes in polymers has been given consideration. The temp
erature dependencies of the decay rate and the kinetic isotope effect
were found at 77-180 K. The controlling factor in the kinetic nonequiv
alence of carbenes is the distribution of distances of the hydrogen at
om tunneling from the matrix molecules. The effect of magnetic field o
n the rate of the carbene decay has been seen at 77 K. On the basis of
the magnetic dependence view, the mechanism of the carbene decay invo
lving spin and chemical dynamics of intermediate short-lived radical p
airs has been advanced, The nature of magnetic effect in polymers show
s the configuration inhomogeneity of radical pairs.