Get Advances in Electrochemical Science and Engineering, Volume PDF

By Richard C. Alkire, Charles W. Tobias

ISBN-10: 352729385X

ISBN-13: 9783527293858

ISBN-10: 3527616799

ISBN-13: 9783527616794

ISBN-10: 3527616888

ISBN-13: 9783527616886

This sequence, previously edited through Heinz Gerischer and Charls V. Tobias, now edited through Richard C. Alkire and Dieter M. Kolb, has been warmly welcomed via scientists world-wide that is mirrored within the experiences of the former volumes:

'This is a vital ebook for researchers in electrochemistry; it covers components of either basic and useful value, with reports of top quality. the fabric is especially good awarded and the alternative of issues displays a balanced editorial coverage that's welcomed.' The Analyst

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Example text

In this theory the dynamics of intramolecular as well as solvent motions have no influence on the rate constant of the reaction. The formation of some favorable geometry of reactant(s), which allows reaction, is fast compared to the intrinsic electron transfer step. In conjunction with this "frozen-reactant'' approximation, the assumption is made that the orientation of the reactant(s) can be regarded as fixed. This is justified if the electron hopping frequency, expressed by the pre-exponential factors in Eqs.

23 eV. 64eV for anthracene, acridine, pyrene, fluoranthene, and naphthalene, respectively [ 1021) can be accessed. The other locally excited states cannot be directly populated, because their energy levels are much higher than the Gibbs energies for the annihilation of radical ions. In a similar way AGCTSand AGc, for reactions (62) and (63) may be evaluated, if the corresponding energies of both (singlet and triplet) excited intramolecular chargetransfer states are available. The energy of these states can be expressed as follows [ 149-15 I] : where w(rin) is the Coulomb energy that is gained when the two ions (A- and D+) are brought together (with the separation distance rin).

Kapturkiewicz isolated ions activated complex locally excited states AG3 excited intramolecular charge-transfer states triplet singlet 3(d-D) hC7f *Go €3 A-D studied, and according to Eq. Thus the expected values of AGcT~and AGcTT should be nearly equal to zero (AGCTS% AGc, E? AGc, M 0). Analysis of the charge-transfer absorption and emission bands leads to the same conclusion [138]. The energy of the emissive intramolecular charge-transfer state may also be estimated by considering the energy of the Franck-Condon ground state reached in the emission.

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Advances in Electrochemical Science and Engineering, Volume 5 by Richard C. Alkire, Charles W. Tobias


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