Electron transfer calculations

Taylor, Scattering Theory The Quantum Theory on Non-relativistic Collisions, Wiley, New York, 1972, pp. 182-185. 

for example, L. A. Collins and D. W. Norcross, Phys. Rev. A, 1978, 18, 467-498, which gives a clear discussion of the subject with many references to earlier work. 

Bull Am. Phys. Soc., 1990, 35, 1822 P. C. Cosby and H. Helm, Wright Laboratory Report No. WL-TR-93-2004, U.S. Air Force Material Command, Wright Patterson AFB, OH 45433-7650, 1993. 

6 The Importance of Interactions That Skip Over Bonds 834 

A acceptor B = bridge D = donor EA = electron affinity EcT = electronic energy transfer ET = electron transfer ETS = electron transmission spectroscopy PES = photoelectron spectroscopy TB = through-bond TS = through-space. 

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Figrue BE 16.20 shows spectra of DQ m a solution of TXlOO, a neutral surfactant, as a function of delay time. The spectra are qualitatively similar to those obtained in ethanol solution. At early delay times, the polarization is largely TM while RPM increases at later delay times. The early TM indicates that the reaction involves ZnTPPS triplets while the A/E RPM at later delay times is produced by triplet excited-state electron transfer. Calculation of relaxation times from spectral data indicates that in this case the ZnTPPS porphyrin molecules are in the micelle, although some may also be in the hydrophobic mantle of the micelle. Furtlier,... 

Balabin I A and Onuchic J N 1998 A new framework for electron-transfer calculations—beyond the pathways-like models J. Phys. Chem. B 10 7497-505... 

Distances, if, of electron transfer calculated using eqn. (26) from the rate constants, k,., of e q reactions with various acceptors and the diffusion coefficients, D, of the reagents 1109,110 ]... 

Fig. 4.30 Influence of the inverse of the equilibrium constant (K) on DDPV curves for a CE mechanism (filled circle) and an EC mechanism open circle) calculated from Eqs. (4.246)-(4.247). K values are marked on the curves.= 102, AE = —50 mV. ti = 1 s, ti/t2 = 20. The DDPV response corresponding to a simple reversible electron transfer calculated from Eq. (4.81) is also plotted blue line). Taken from [77] with permission...

The rate constants k24 for biphenyl, t-stilbene, m-terphenyl, and naphthalene vary between 2.5 x lO M s and 7.9 x lO M s (Table 4). The driving forces (-AG) of the bimolecular electron transfer, calculated on the basis of the difference in the respective arenes and fullerenes ionization potentials (-AG = AIP = IParene IPfuiierene) show no linear correlation with the measured rate constants for the electron transfer reactions. In fact, it is interesting to note that these results indicate even a decrease of the rate constant at higher AIP s. 

Thus an explicit expression for the rate constants can be obtained. The above treatment, however, neglects changes in the bond distances and bond angles in the inner coordination shells of the reactants during electron transfer. Calculation of the free energy for this process requires a detailed knowledge of the potential energy for vibrational displacements, i.e., the force constants and displacements associated with vibrational modes. Inclusion of this factor adds to Aq a term, A,-, which is a function of force constants and vibrational displacements. 

Atoms in Molecules Electron Transfer Calculations Electronic Wavefunctions Analysis Hyperconjugation Intermolecular Interactions by Perturbation Theory Localized MO SCF Methods Natural Orbitals NMR Chemical Shift Computation Ab Initio Rotational Barriers Barrier Origins Valence Bond Curve Crossing Models. 

Michael N. Paddon-Row University of New South Wales, Sydney, Australia Electron Transfer Calculations 2 826... 

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