Total reorganization energy

In this equation, 2 is the total reorganization energy given by... 

Figure 1. Activation energy of electron-transfer process as a function of electronic energy gap of a reaction. Er = Eg + Ec is the total reorganization energy where Es is the classical solvent reorganization energy and Ec is the reorganization energy of an intramolecular mode, l

Figure 2. Deuterium isotope effect for electron transfer between ammine complexes as a function of the reduced electronic energy gap AE/EC where Er is the total reorganization energy E, = Eg + Ec. Key for parameters — —, hci)H/kBT — 2.0 and Es/Ec = 0 ------------------, Es/Ec = 1 and-------, Es/Ec = 2.

E = hv. In Figure 5 we show a plot of E vs total reorganization energy for various values of the electronic coupling. The... 

Figure 5. Mean band energy (E) vs. total reorganization energy [Eq. (18)]. The dashed curve is the equation, E = Et. The solid curves are calculated from an analytical expression (9). The solid dots are calculated from a diagonalization of the two-mode model secular determinant with c = —6.0, Ac, = 1.1, and vc, =...

Depending on the solvent polarity and redox potentials of a donor and an acceptor, the ions resulting from electron transfer may remain associated either as a contact IRP or as a solvent-separated IRP. In the contact pair, back electron transfer can take place. For such electron back-transfers, the solvent reorganization energy is less than 5% of the total reorganization energy (Serpa and Arnaut 2000). 

The total reorganization energy is equal to the free energy change for an activationless electron transfer reaction (40-48). In Marcus theory (48,53) this condition is expressed as AG -X, where... 

The total reorganization energy >. in classical Marcus theory was estimated by the method described below. A plot of the maximum of the IPCT band in solution (T op) against the driving force of electron transfer within the contact... 

FIGURE 15. Potential energy surfaces for the ground state DA), the excited state DA, reactant state), and the charge-separated state D+-A, product state), proposed by Marcus s theory. X, total reorganization energy TS, transition state. (Modified from Ref. 19.)... 

The character of the rate constant vs — AG° dependence observed in Ref. [259] for electron transfer from BPh to QA was quantitatively explained in terms of Eq. (23) assuming that (1) vibrations with ha 100 meV are coupled to electron transfer, the total reorganization energy, Er for these vibrations being 600 + 100 eV (2) vibrations with fico 15 meV are coupled to electron transfer (3) Er for the vibrations with ha < 1 meV being less than 300 meV. 

Figure 2 Plots of log vs. AGg-j- calculated by using theory. Solid line calculated by using semiclassical theory [Eq. (4), see text] and dashed line calculated by using quantum theory [Eq. (5)]. Rate maximum occurs when the total reorganization energy (X) is equal to the driving force (e.g., when X = IAGCTI).

The total reorganization energy AGFC will in general be made up of three components, which we may call the bonding, the ligand, and the solvent terms ... 

In spite of those difficulties, generalizations can be easily made. The onset of the inverted region starts around 1.5-2 eV of driving force (corresponds to 2j + As). The value of V is small (10-20 cm-1), and the solvent reorganization energy is the dominant component of the total reorganization energy. An increase in size of the aromatic system leads to a decrease in V and 2S, but the... 

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