Microcanonical time correlated

By far the most common methods of studying aqueous interfaces by simulations are the Metropolis Monte Carlo (MC) technique and the classical molecular dynamics (MD) techniques. They will not be described here in detail, because several excellent textbooks and proceedings volumes (e.g., [2-8]) on the subject are available. In brief, the stochastic MC technique generates microscopic configurations of the system in the canonical (NYT) ensemble the deterministic MD method solves Newton s equations of motion and generates a time-correlated sequence of configurations in the microcanonical (NVE) ensemble. Structural and thermodynamic properties are accessible by both methods the MD method provides additional information about the microscopic dynamics of the system. 

At present the body of data on reactions in clusters is insufficient to test the above two microcanonical approaches. For electron transfers in solution it seems clear that the vibrational assistance approach, stemming from Eq. (1.2), with its extensions mentioned earlier, is the one that has been the most successful [27-30]. For slow isomerizations Sumi and Asano have pointed out that an analysis based on Eq. (1.2) was again needed [40]. An approach based on Eq. (1.1) or on its extension to include a frequency-dependent friction, they noted, led to unphysical correlation times [40]. In investigations of fast isomerizations the most commonly studied system has been the photoex-cited trans-stilbene [5, 41-43,46]. Difficulties encountered by a one-coordinate treatment for that system have been reported [4, 8]. Indeed, coherence results for photoexcited cw-stilbene have shown a coupling of a phenyl torsional mode to the torsional mode about the C=C bond [42, 47]. 

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