Electron solvation energy

On correcting to unit activity Ag (aq), we can obtain E g/Ag - Electron solvation energy is neglected in this definition. 

Let us discuss now the conditions required for the electron transfer process. This reaction requires, of course, a suitable electron donor (a species characterized by a low ionization potential) and a proper electron acceptor, e.g., a monomer characterized by a high electron affinity. Furthermore, the nature of the solvent is often critical for such a reaction. The solvation energy of ions contributes substantially to the heat of reaction, hence the reaction might occur in a strong solvating solvent, but its course may be reversed in a poorly solvating medium. A good example of this behavior is provided by the reaction Na -f- naphthalene -> Na+ + naphthalene". This reaction proceeds rapidly in tetrahydrofuran or in dimethoxy... 

A. Frumkin, and B. Damaskin, Real free solvation energy of an electron in a solution in equilibrium with the electrode and its dependence on the solvent nature,/. Electroanal. Chem. 79, 259-266 (1977). 

For electron transfer to and from a metal to species in solution the situation is complicated by the solvation energy of the species and in the general case changes in adsorption energy caused by electron transfer may also have to be taken into account. If we consider a simple reaction... 

Until now, the overwhelming majority of disproportionations of larger molecules studied have concerned conjugated systems. Since all respective oxidation levels possess the same number of a bonds, consideration can be restricted to rr-electron energies. In solution, however, solvation energy should be taken into account. 

As for the theoretical treatment, we could only try to include the eleetrostatie solute-solvent interaetions and, in faet, we corrected the electronic potential energies for the solvation effeets by simply adding as calculated according to the solvaton model [eq. (2)]. The resulting potential curves are to be seen as effective potentials at equilibrium, i.e. refleeting orientational equilibrium distributions of the solvent dipoles around the eharged atoms of the solute molecule. In principle, the use of potentials thus corrected involves the assumption that solvent equilibration is more rapid than internal rotation of the solute molecule. Fig. 4 points out the effects produced on the potential... 

Photoinduced ET at liquid-liquid interfaces has been widely recognized as a model system for natural photosynthesis and heterogeneous photocatalysis [114-119]. One of the key aspects of photochemical reactions in these systems is that the efficiency of product separation can be enhanced by differences in solvation energy, diminishing the probability of a back electron-transfer process (see Fig. 11). For instance, Brugger and Gratzel reported that the efficiency of the photoreduction of the amphiphilic methyl viologen by Ru(bpy)3+ is effectively enhanced in the presence of cationic micelles formed by cetyltrimethylammonium chloride [120]. Flash photolysis studies indicated that while the kinetics of the photoinduced reaction,... 

Kamlet, M. J., M. E. Jones, J.-L. M. Abboud, and R. W. Taft. 1979. Linear Solvation Energy Relationships. Part 2. Correlations of Electronic Spectral Data for Aniline Indicators with Solvent tt and 3 Values. J. Chem. Soc., Perkins Trans. 2, 342. 

Marchi, M. Sprik, M. Klein, M. L., Calculation of the free energy of electron solvation in liquid ammonia using a path integral quantum Monte Carlo simulation, J. Phys. Chem. 1988, 92, 3625-3629... 

In the Bom like approaches to solvation energy, the electrostatic potential of the ion appears as the basic variable of the theory. From Eq (1), it may be seen that if we have accurate electron densities at hand, the electrostatic potential strongly depends on the ionic radius r. The choice of suitable ionic radii usually introduces some arbitrariness in the calculation of AESolv there is no a physical criterium to justify the use of empirical rA values coming from different sources [15-16],... 

The article is organized as follows in Section 2, a general discussion concerning the definition of electrostatic potentials in the frame of DFT is presented. In Section 3, the solvation energy is reformulated from a model based on isoelectronic processes at nucleus. The variational formulation of the insertion energy naturally leads to an energy functional, which is expressed in terms of the variation of the electron density with respect to... 

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