Phase space theory orbiting transition state

Phase space theory can be thought of as, in effect, considering a loose or, as it is sometimes called, orbiting [333] transition state regardless of the nature of the reaction. The need to select transition state properties for each individual reaction considered is avoided and it has been argued that a virtue of the theory is that it gives definite predictions [452]. 

Recent mechanistic discussions of unimolecular decompositions of organic ions have invoked ion—molecule complexes as reaction intermediates [102, 105, 361, 634]. The complexes are proposed to be bound by long-range ion—dipole forces and to be sufficiently long-lived to allow hydrogen rearrangements to occur. The question of lifetime aside, there is more than a close similarity between the proposed ion—dipole intermediate and the assumed loose or orbiting transition state of phase space theory. 

PHASE SPACE THEORY AND ORBITING TRANSITION STATE PHASE SPACE THEORY... 

Orbiting Transition State Phase Space Theory... 

Chesnavich and Bowers (1977a,b 1979) modified the phase space theory model by assuming (a) an orbiting transition state located at the centrifugal barrier, and (b) that orbital rotational energy at this transition state is converted into relative translational energy of the products. The Hamiltonian used for this orbiting transition state/phase... 

Figure 11. Kinetic energy release distribution for metastable loss of CH4 from nascent Co(C3Hg)+ collision complexes. The "unrestricted" phase space theory curve assumes the entrance channel contains only an orbiting transition state, the exit channel has only an orbiting transition state (no reverse activation barrier), and there are no intermediate tight transition states that affect the dynamics. The "restricted" phase space theory calculation includes a tight transition state for insertion into a C-H bond located 0.08 eV below the asymptotic energy of the reactants.

For the theoretician, clusters are also convenient model systems to evaluate the performance of dissociation rate theories. By comparing the results of numerically exact molecular dynamics (MD) trajectories to the predictions of rate theories, the various approximations inherent to these theories can be unambiguously tested and possibly improved upon. Previous authors have critically discussed how the Rice-Ramsperger-Kassel (RRK), ° Weisskopf, and Phase Space Theory of Light and Pechukas, Nikitin, Klots, Chesnavich and Bowers respectively compare for the thermal evaporation of atomic clusters. This work was subsequently extended by the present authors to rotating and molecular clusters. From these efforts it was concluded that phase space theory (PST), in its orbiting transition state version, was quantitatively able to describe statistical dissociation. This chapter is not devoted to a detailed presentation of phase space theory and the reader is encouraged to consult the cited work. 

Variations of the evaporation rate constant of the (H2O)50 cluster, as predicted by phase space theory (PST) in its orbiting transition state version, and values of the rate constant obtained from statistical molecular dynamics (MD) trajectories at high energies. The inset shows the decay of the number of clusters N(t) having resisted evaporation as a function of time, at three internal energies denoted next to the curves and in logarithmic scale. 

The orbiting transition state phase space theory (OTS/PST)... 

Phase space orbiting transition state theory works much better for the calculation of KERDs than for that of the rate constants, thereby demonstrating that the former are controlled by the long-range part of the potential whereas the latter are governed by its shorter range. In addition, Klots has introduced a set of effective temperatures to parametrize the observed distributions. The SACM has also demonstrated its usefulness in the case of weakly bonded species. 

In the conventional theory, a saddle with index 1 corresponds to a transition state. Near a saddle, the NHIM Mq exists above it in the phase space. The NHIM Mo consists of those orbits with q = 0 and p = 0—that is, the vibrational motions involving qn,Pn) for n = 2,...,N above the saddle. Thus, its... 

Oped a so-called reactive island theory the reactive islands are the phase-space areas surrounded by the periodic orbits in the transition state, and reactions are interpreted as occurring along cylindrical invariant manifolds through the islands. Fair et al. [29] also found in their two- and three-dof models of the dissociation reaction of hydrazoic acid that a similar cylinderlike structure emerges in the phase space as it leaves the transition state. However, these are crucially based on the findings and the existence of (pure) periodic orbits for all the dof, at least in the transition states. Hence, some questions remain unresolved, for example, How can one extract these periodic orbits from many-body dof phase space and How can the periodic orbits persist at high energies above the saddle point, where chaos may wipe out any of them ... 

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