Reorganization energy defined

The other model parameters entering Eq. [66] are the nuclear reorganization energies defined through the second cumulants of the reaction coordinate... 

A schematic view of the two potential surfaces projected onto a single normal mode is seen in Fig. 12.3. The normal mode shifts express the deviation of the equilibrium configuration of electronic state from some specified reference configuration (e.g. the ground state equilibrium), projected onto the normal mode directions. Other useful parameters are the single mode reorganization energy defined by the inset to Fig. 12.3,... 

Reaction scheme, defined, 9 Reactions back, 26 branching, 189 chain, 181-182, 187-189 competition, 105. 106 concurrent, 58-64 consecutive, 70, 130 diffusion-controlled, 199-202 elementary, 2, 4, 5, 12, 55 exchange, kinetics of, 55-58, 176 induced, 102 opposing, 49-55 oscillating, 190-192 parallel, 58-64, 129 product-catalyzed, 36-37 reversible, 46-55 termination, 182 trapping, 2, 102, 126 Reactivity, 112 Reactivity pattern, 106 Reactivity-selectivity principle, 238 Relaxation kinetics, 52, 257 -260 Relaxation time, 257 Reorganization energy, 241 Reversible reactions, 46-55 concentration-jump technique for, 52-55... 

In Eq. (77), x = h(o/2kg T is the reduced internal frequency, q = EJhoi the reduced solvent reorganization energy, p = hElha> the reduced electronic energy gap and / (z) the modified Bessel function of order m. The quantity S is a coupling parameter which defines the contribution of the change in the internal normal mode ... 

For the transition description, the phonon system may be replaced by one effective vibration mode. We obtained the expressions for the transition probability as a function of the temperature and the difference of electron energies, and the most important parameter that defined this dependence is reorganization energy of the vibration system. The transition probability, or the rate constant, has the form of thermo-activation exponent at high temperatures. 

Focusing on As, we note that in effect, the discrete coordinate shift Ax > (defined below Equation (3.77)) is replaced here by the continuum coordinate shift D(Ap), in which Z)(Ap) 2 is proportional to a reorganization energy density (per unit volume) [39], Equation (3.89) is a generalization of Equation (3.88), in which D is a function of the dielectric constant (i.e., with inclusion of the image effects neglected in Equation (3.88) [12,22]) ... 

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