Unimolecular reaction dynamics

Baer T and Fiase W L (eds) 1996 Unimolecular Reaction Dynamics (Qxford Qxford University Press)... 

Hase W L and Buckowski D G 1982 Dynamics of ethyl radical decomposition. II. Applicability of classical mechanics to large-molecule unimolecular reaction dynamics J. Comp. Chem. 3 335-43... 

Polik W F, Guyer D R, Miller W H and Moore C B 1990 Eigenstate-resolved unimolecular reaction dynamics ergodic character of Sq formaldehyde at the dissociation threshold J. Chem. Phys. 92 3471-84... 

Waite B A and Miller W H 1980 Model studies of mode specificity in unimolecular reaction dynamics J. Chem. Phys. 73 3713-21... 

Baer T and Hase W L 1996 Unimolecular Reaction Dynamics. Theory and Experiments (New York Oxford University Press) Tliompson D L 1999 Int. Rev. Rhys. Chem. 17 547-69... 

He Y, Pochert J, Quack M, Ranz R and Seyfang G 1995 Discussion contributions on unimolecular reactions dynamics J. Chem. Soc. Faraday Discuss. 102 358-62, 372-5... 

C3.3.5.1 MASTER EQUATION ANALYSIS OF UNIMOLECULAR REACTION DYNAMICS... 

Baer T and Flase W L 1996 Unimolecular Reaction Dynamics Theory and Experiments (Oxford)... 

T. Baer and W. L. Hase, Unimolecular Reaction Dynamics, Oxford University Press, New York, 1996. 

D. Shemesh, S. L. Blair, S. A. Nizkorodov, R. B. Gerber. Photochemistry of aldehyde clusters cross-molecular versus unimolecular reaction dynamics, Phys. Chem. Chem. Phys., 16 23861-23868 (2014). 

The knowledge of the two-minima energy surface is sufficient theoretically to determine the microscopic and static rate of reaction of a charge transfer in relation to a geometric variation of the molecule. In practice, the experimental study of the charge-transfer reactions in solution leads to a macroscopic reaction rate that characterizes the dynamics of the intramolecular motion of the solute molecule within the environment of the solvent molecules. Stochastic chemical reaction models restricted to the one-dimensional case are commonly used to establish the dynamical description. Therefore, it is of importance to recall (1) the fundamental properties of the stochastic processes under the Markov assumption that found the analysis of the unimolecular reaction dynamics and the Langevin-Fokker-Planck method, (2) the conditions of validity of the well-known Kramers results and their extension to the non-Markovian effects, and (3) the situation of a reaction in the absence of a potential barrier. 

Crim, F.F. (1984). Selective excitation studies of unimolecular reaction dynamics, Ann. Rev. Phys. Chem. 35, 657-691. 

TYoe, J. (1988). Unimolecular reaction dynamics on ab initio potential energy surfaces, Ber. Bunsenges. Phys. Chem. 92, 242-252. 

Thus, it is clear what is meant by the words apparent unimolecular reaction, since the activation process can be bimolecular. A key point is the separation in time scales between the activation step and the subsequent unimolecular reaction dynamics. This was also a distinctive feature of the indirect photo-activated reactions considered in the previous section. Thus, the theoretical description of these reaction types is very similar photo-activation makes it, in particular, possible to deposit a precise amount of energy according to E = hi/. 

T. Baer and W.L. Hase, Unimolecular reaction dynamics. Theory and experiments (Oxford, 1996)... 

This hnding concerning quantum transport in classically chaotic systems sheds new light on quantum effects in unimolecular reaction dynamics. For example, one expects that intramolecular bottlenecks associated with canton, if treated quantum mechanically, would be more effective than in a classical statistical theory even when nh is smaller than the reaction flux crossing the intramolecular dividing surface. Clearly, it would be interesting to examine realistic molecular systems in a similar fashion. 

P J. Robinson and Holbrook, Unimolecular Reactions, John Wiley Sons, London, 1972 W. Forst, Theory of Unimolecular Reactions, Academic, New York, 1972 T. Baer and W. L. Hase, Unimolecular Reaction Dynamics Theory and Experiments, Oxford, New York, 1996. 

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