State Preparation and Intramolecular Vibrational Energy Redistribution

The first step in a unimolecular reaction involves energizing the reactant molecule above its decomposition threshold. An accurate description of the ensuing unimolecular reaction requires an understanding of the state prepared by this energization process. In the first part of this chapter experimental procedures for energizing a reactant molecule are reviewed. This is followed by a description of the vibrational/rotational states prepared for both small and large molecules. For many experimental situations a superposition state is prepared, so that intramolecular vibrational energy redistribution (IVR) may occur (Parmenter, 1982). IVR is first discussed quantum mechanically from both time-dependent and time-independent perspectives. The chapter ends with a discussion of classical trajectory studies of IVR. 

A number of different experimental methods have been used to energize a unimolecular reactant. Energization can take place by transfer of energy in a bimolecular collision, as in 

Another method which involves molecular collisions is chemical activation. Here the excited unimolecular reactant is prepared by the potential energy released in a reactive collision such as 

The excited C2H4F molecule can redissociate to the reactants F + C2H4 or form the new products H + C2H3F. 

HjCOfSo) + hv- H2CO(5i) HjCO fSo) - H2 + CO. Here, Sg and Sj represent the ground and first excited singlet states. 

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Dynaniical theories of unimolecuiar decomposition deal with the properties of vibrational/rotational energy levels, state preparation and intramolecular vibrational energy redistribution (IVR). Thus, the presentation in this chapter draws extensively on the previous chapters 2 and 4. Unimolecuiar decomposition d)mamics can be treated using quantum and classical mechanics, and both perspectives are considered here. The role of nonadiabatic electronic transitions in unimolecuiar dynamics is also discussed. 

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