Lifetimes, quantum dynamical calculation

Recently the two-step decomposition of azomethane was proved in the study of the femtosecond dynamics of this reaction [68]. The intermediate CH3N2 radical was detected and isolated in time. The reaction was found to occur via the occurrence of the first and the second C—N bond breakages. The lifetime of CH3N2 radical is very short, i.e., 70fsec. The quantum-chemical calculations of cis- and /nmv-azomcthanc dissociation was performed [69]. 

Trim-ethylene is a moiety with a shallow potential energy well on the reaction path connecting cyclopropane and propylene. Its very short unimolecular lifetime, following different types of initial excitations, has been calculated from classical trajectories [343,344] and compared with both experiment [391] and quantum dynamics [392]. Excellent agreement is found. This is an example of a rather large molecule, for which classical mechanics accurately describes the unimolecular dissociation because of the shallow potential energy minimum and, thus, very short lifetime. 

The random lifetime assumption is perhaps most easily tested by classical trajectory calculations (Bunker, 1962 1964 Bunker and Hase, 1973). Initial momenta and coordinates for the Hamiltonian of an excited molecule can be selected randomly, so that a microcanonical ensemble of states is selected. Solving Hamilton s equations of motion, Eq. (2.9), for an initial condition gives the time required for the system to reach the transition state. If the unimolecular dynamics of the molecule are in accord with RRKM theory, the decomposition probability of the molecule versus time, determined on the basis of many initial conditions, will be exponential with the RRKM rate constant. That is, the decay is proportional to exp[-k( )t]. The observation of such an exponential distribution of lifetimes has been identified as intrinsic RRKM behavior. If a microcanonical ensemble is not maintained during the unimolecular decomposition (i.e., IVR is slower than decomposition), the decomposition probability will be nonexponential, or exponential with a rate constant that differs from that predicted by RRKM theory. The implication of such trajectory studies to experiments and their relationship to quantum dynamics is discussed in detail in chapter 8. 

The quantum alternative for the description of the vibrational degrees of freedom has been commented by Westlund et al. (85). The comments indicate that, to get a reasonable description of the field-dependent electron spin relaxation caused by the quantum vibrations, one needs to consider the first as well as the second order coupling between the spin and the vibrational modes in the ZFS interaction, and to take into account the lifetime of a vibrational state, Tw, as well as the time constant,T2V, associated with a width of vibrational transitions. A model of nuclear spin relaxation, including the electron spin subsystem coupled to a quantum vibrational bath, has been proposed (7d5). The contributions of the T2V and Tw vibrational relaxation (associated with the linear and the quadratic term in the Taylor expansion of the ZFS tensor, respectively) to the electron spin relaxation was considered. The description of the electron spin dynamics was included in the calculations of the PRE by the SBM approach, as well as in the framework of the general slow-motion theory, with appropriate modifications. The theoretical predictions were compared once again with the experimental PRE values for the Ni(H20)g complex in aqueous solution. This work can be treated as a quantum-mechanical counterpart of the classical approach presented in the paper by Kruk and Kowalewski (161). 

Quantum Theory of Scattering and Unimolecnlar Breakdown.—From the theoretical viewpoint it would appear natural to compute lifetimes and cross-sections for unimolecular processes like equation (34) by one of the existing methods for the solution of the set of coupled equations of the scattering problem. There have been, however, hardly any calculations for experimental examples or at least realistic model systems. The present status of the quantum theory of unimolecular reactions is still rather in the domain of formal theories or hi y simplified models, which are not of immediate interest to the experimentalist. We shall, nevertheless, review some of the recent developments, because one may hope that in the future the detailed dynamical theories will provide a deeper understanding of unimolecular dynamics than the statistical theories presently do. 

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