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By Seib P.A., Tolbert B.M. (eds.)

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Second, the one-dimensional model for a tunneling reaction in the solid phase is described briefly in Sect. 3. Third, since the tunneling reactions in the solid phase should be treated by taking into consideration the intermolecular vibration of reactants, the multi-dimensional model for a tunneling reaction in the solid phase is described in Sect. 4. The rate constant is based upon the Fermi golden rule, in which the tunneling is considered as the transition from the initial state to the final state.

1972) significantly differs from the experimental one. The continuation of the investigations of H-atom abstraction in alcohol matrices appeared in the work ofLe Roy et al. (1980). 2 K. The results of the measurements are very similar to the temperature dependence described by Hudson et al. (1977). At the same time, an attempt was made to describe the temperature dependence for five tunneling reactions between a methyl radical and matrix molecules on the basis of thermal population of the upper vibrational levels in the initial potential well.

In the case of a weak reagent interaction with the medium, the rate of the isomerization will increase with increasing viscosity (pressure). With further increase in viscosity, the reorganization of the reagents and medium becomes the rate determining step of the reaction. Indeed, during the isomerization the molecule changes its configuration, and as a result the rearrangement of neighboring molecules occurs. The activation energy of the process increases with increasing viscosity (pressure), which leads to a decrease of the isomerization rate.

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