Cage effect dynamics

Cage effect dynamics or kinetics of geminate recombination was observed for the first time under photodissociation of aC C dimer of aromatic radicals in a viscous media. A suggestion has been made that at least in a number of smdied cases the mumal diffusion coefficient of radicals in the pair is approximately 10 times lower than the sum of macroscopic diffusion coefficients of the individual species. In other words, a geminate recombination proceeds considerably longer than expected. 

Cage Effect The cage effect dynamics after excitation of the photoinitiator has been studied [261 ]. In fact, the radicals generated upon cleavage or amine interaction constitute a triplet radical pair that readily dissociate into free radicals in nonviscous media. In a viscous medium, the radical pair undergoes intersystem... 

Wang W, Nelson K A, Xiao L and Coker D F 1994 Molecular dynamics simulation studies of solvent cage effects on photodissociation in condensed phases J. Chem. Phys. 101 9663-71... 

Molecular-Dynamics Simulation of a Glassy Polymer Melt Rouse Model and Cage Effect. 

The simulations demonstrated, that after the pump excitation of the iodine molecules into their B state three elementary dynamical processes determine the further reaction course (i) the predissociation of the iodine molecules caused by the coupling of the electronic B state to the repulsive ajo states, (ii) the electronic transitions from these states to the A, A, and X states due to the caging effect, and (iii) the vibrational relaxation in all electronic states involved in the reaction. Additionally, an energy shift of the potential curves due to the influence of the crystalline DDR cage could be observed. 

Note, as in the discussed case of the ns photoionization cross sections of Mg, Ca, Sr and Ba, the presented pfsAa and pfsAb parameters for Hg must be corrected by accounting for the dynamical-cage effect, since the... 

The rebinding dynamics to microperoxidase are nonexponential due to a solvent cage effect. To deduce the time constant for rebinding CO from the solvent cage, the recombination kinetics were modeled according to... 

In a second example the discrete time-reversible propagation scheme for mixed quantum-classical dynamics is applied to simulate the photoexcitation process of I2 immersed in a solid Ar matrix initiated by a femtosecond laser puls. This system serves as a prototypical model in experiment and theory for the understanding of photoinduced condensed phase chemical reactions and the accompanied phenomena like the cage effect and vibrational energy relaxation. It turns out that the energy transfer between the quantum manifolds as well as the transfer from the quantum system to the classical one (and back) can be very well described within the mixed mode frame outlined above. 

---