No abstract available

[en] This manuscript details the observation of electron solvation by a two-dimensional interface

[en] The absorption of the solvated electron was measured to appear less than 0.3 ps after photolysis of aqueous ferrocyanide solutions with subpicosecond ultraviolet pulses. This upper limit for the electron solvation time in water suggests a mechanism involving pre-existing deep traps, rather than known mechanisms requiring molecular reorientation. (orig.)

[en] An improved method is developed for calculation of relaxation times for dipole orientation in liquid alcohols induced by localized excess electrons. The dielectric relaxation of the medium beyond the first solvation shell of the electron is explicitly incorporated. Results are presented for methanol, ethanol, and 1-propanol and compared to recent experiments. Although this increases the calculated relaxation times compared to calculations neglecting medium relaxation, the improvement in comparison with experimental values is small. This implies that orientational relaxation of molecular dipoles in the first solvation shell around a localized electron proceeds first and then the dielectric relaxation of the medium beyond the first solvations shell occurs to complete the electron solvation. The calculated temperature dependence for electron solvation in 1-propanol is non-Arrhenius and fits well with recent experimental data

[en] The ultrasonic velocity in non-aqueous electrolytic solutions has been measured which gives valuable information regarding the nature and strength of various interactions and the formation of hydrogen bonding. It also shows the behaviour of hydrogen such as molecular association and dissociation. Solvation is the association of solvent molecules with the solute ions in a solution. In the present study, the fundamental parameters of three amino acids namely, -arginine, -arginine mono hydrochloride and -arginine methyl ester dihydrocholoride in non-aqueous solution as a function of composition in the temperature range 278.15-328.15 K have been measured. Using these experimental value solvation number and the acoustical parameters such as adiabatic compressibility, apparent molal volume and apparent molal compressibility have been calculated for all the three systems. These results are analysed and eventually emphasizing the possible molecular interactions in terms of structure-making and structure-breaking effects of the above amino acids in the solvent. (author)

[en] Most recent advances in time-resolved studies of solvation of excess electron and its geminate recombination in polar liquid in the picosecond to subpicosecond time domain has been reviewed. Emphasis is given on the applicability of two-state model of solvation of this species. Potentiality of Feynman path integral technique and SCF-X^α-SW technique to describe absorption spectrum of this species has been indicated. (author)

No abstract available

[en] In this chapter the authors address only the final state of the electron, that is, the solvated state, which, if no chemical reaction would occur, is a stable entity with well-defined characteristics. Except for some metal-ammonia solutions, and possible a few other cases, such stable species, in reality, exist but a short time (often as short as microseconds). Nevertheless, this chapter only deals with this final time-independent,'' completely solvated,'' equilibrium species. The last statement is added to indicate that the solvent around the electron has also come to thermal equilibrium with the field of the charge

[en] Pulse radiolytic techniques have been used to measure the solvation of anions and electrons in alcohols. The results have shown the importance of the microscopic liquid structure in the solvation process. The activation energy for benzophenone solvation is equal to the hydrogen-bond energy for the liquids, which shows that the solvent reorganization requires the breaking of the hydrogen bonds between solvent molecules. For electron solvation, primary alcohols have a lower activation energy because the initial hydrogen-bonded structure of the liquid is amenable to solvation. The solvation of an electron in a secondary alcohol requires require hydrogen-bond breakage

[en] The one-electron reduction product of nitrate, the NO₃^2- radical, was reinvestigated because of the contemporary interest in its reactivity in high-level liquid radioactive systems. Indirect observations suggest that the same dianion is produced by the precursor to the solvated electron. The redox potential of the couple NO₃^-/NO₃^2- was calculated, using several ab initio approaches combined with semiempirical solvation models, to be E^o ∼ -1.1 V vs NHE. Using the theoretical prediction to guide the experiment, we find a value of E^o = -0.89 V at zero ionic strength. Kinetic and free-energy-relationship arguments are used to question the acid-base equilibria and reaction mode that converts the NO₃^2- to the oxidizing NO₂ radical. It is proposed that the reaction of the dianion with various general acids is an O^2- (i.e., water or OH^-) transfer to the acid and not proton transfer to NO₃^2-. Implications of the highly negative redox potential of the dianion and the existence of the protonated forms to practical systems are discussed.