Marcus

J. A. Marinsky and Y. Marcus, eds.. Ion Exchange and Solvent Extraction, Marcel Dekker, New York, 1973. 

Khundkar L R, Marcus R A and Zewail A H 1983 Unimolecular reactions at low energies and RRKM-behaviour isomerization and dissociation J. Phys. Chem. 87 2473-6... 

Marcus P, Teissier A and Oudar J 1984 The influence of sulfur on the dissolution and the passivation of a nickel-iron alloy. 1. Electrochemical and radiotracer measurements Corrosion Sc . 24 259... 

For imiltidiniensional problems, the generalization of WKB theory to the description of scattering problems is often called Miller-Marcus or classical. S-niatrix theory [ ]. The reader is refened to review articles for a more complete description of this theory [52]. 

Marcus R A 1970 Extension of the WKB method to wave functions and transition probability amplitudes (S-matrix) for inelastic or reactive collisions Chem. Phys. Lett. 7 525-32... 

In the statistical description of ununolecular kinetics, known as Rice-Ramsperger-Kassel-Marcus (RRKM) theory [4,7,8], it is assumed that complete IVR occurs on a timescale much shorter than that for the unimolecular reaction [9]. Furdiemiore, to identify states of the system as those for the reactant, a dividing surface [10], called a transition state, is placed at the potential energy barrier region of the potential energy surface. The assumption implicit m RRKM theory is described in the next section. 

Marcus R A 1952 Unimolecular dissociations and free radical recombination reactions J. Chem. Rhys. 20 359-64... 

Wardlaw D M and Marcus R A 1984 RRKM reaction rate theory for transition states of any looseness Chem. Rhys. Lett. 110 230-4... 

Klippenstein S J 1992 Variational optimizations in the Rice-Ramsperger-Kassel-Marcus theory calculations for unimolecular dissociations with no reverse barrier J. Chem. Rhys. 96 367-71... 

Marcus R A 1977 Energy distributions in unimolecular reactions Ber. Bunsenges. Phys. Chem. 81 190-7... 

Marcus R A 1973 Semiclassical theory for collisions involving complexes (compound state resonances) and for bound state systems Faraday Discuss. Chem. Soc. 55 34—44... 

The calculation of the time evolution operator in multidimensional systems is a fomiidable task and some results will be discussed in this section. An alternative approach is the calculation of semi-classical dynamics as demonstrated, among others, by Heller [86, 87 and 88], Marcus [89, 90], Taylor [91, 92], Metiu [93, 94] and coworkers (see also [83] as well as the review by Miller [95] for more general aspects of semiclassical dynamics). This method basically consists of replacing the 5-fimction distribution in the true classical calculation by a Gaussian distribution in coordinate space. It allows for a simulation of the vibrational... 

Marcus R A 1983 On the theory of intramolecular energy transfer Faraday Discuss. Chem. Soc. 75 103-15... 

Marcus R A and Rice O K 1951 The kinetics of the recombination of methyl radicals and Iodine... 

Sekiguchi S, Kobori Y, Akiyama K and Tero-Kubota S 1998 Marcus free energy dependence of the sign of exchange interactions in radical ion pairs generated by photoinduced electron transfer reactions J. Am. Chem. Soc. 120 1325-6... 

Marcus R A 1966 On the analytical mechanics of chemical reactions. Quantum mechanics of linear collisions J. Chem. Phys. 45 4500... 

Guldi D M and Asmus K-D 1997 Electron transfer from Cjg D2) and Cjg C2 ) to radical cations of various arenes evidence for the Marcus inverted region J. Am. Chem. See. 119 5744-5... 

Marcus P and Oudar J (ed) 1995 Corrosion Meohanisms in Theory and Praotioe (New York Dekker)... 

Clayton C R and Olefjord I 1995 Corrosion Mechanisms In Theory and Practice ed P Marcus and J Oudar (New York Dekker) p 175... 

Marcus M A ef a/1991 Structure of capped CdSe clusters by EXAFS J. Phys. Chem. 95 1572... 

Modem electron transfer tlieory has its conceptual origins in activated complex tlieory, and in tlieories of nonradiative decay. The analysis by Marcus in tire 1950s provided quantitative connections between the solvent characteristics and tire key parameters controlling tire rate of ET. The Marcus tlieory predicts an adiabatic bimolecular ET rate as... 

Here X is tire reorganization energy associated witli the curvature of tire reactant and product free energy wells and tlieir displacement witli respect to one another. Assuming a stmctureless polarizable medium, Marcus computed the solvent or outer-sphere component of tire reorganization energy to be... 

Here we have treated tlie nuclear degrees of freedom classically as in tlie Marcus foniiulation [1]. 

Early studies showed tliat tire rates of ET are limited by solvation rates for certain barrierless electron transfer reactions. However, more recent studies showed tliat electron-transfer rates can far exceed tire rates of diffusional solvation, which indicate critical roles for intramolecular (high frequency) vibrational mode couplings and inertial solvation. The interiDlay between inter- and intramolecular degrees of freedom is particularly significant in tire Marcus inverted regime [45] (figure C3.2.12)). 

Figure C3.2.12. Experimentally observed electron transfer time in psec (squares) and theoretical electron transfer times (survival times, Tau a and Tau b) predicted by an extended Sumi-Marcus model. For fast solvents tire survival times are a strong Emction of tire characteristic solvent relaxation dynamics. For slower solvents tire electron transfer occurs tlirough tire motion of intramolecular degrees of freedom. From [451.

Marcus R A and Sutin N 1985 Eiectron transfers in chemistry and bioiogy Biochim. Biophys. Acta 811 265-322... 

Gould I R, Ege D, Mattes S L and Farid S 1987 Return electron transfer with geminate radical ion pairs - observation of the Marcus inverted region J. Am. Chem. Soc. 109 3794-6... 

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