Electron aqueous solvation

Sukumar, N., and G. A. Segal. 1986. Effect of Aqueous Solvation upon the Electronic Excitation Spectrum of the Glycine Zwitterion A Theoretical Cl Study Using a Fractional Charge Model. J. Am. Chem. Soc. 108, 6880-6884. 

Schwartz, B. J. and Rossky, P. J. Aqueous solvation dynamics with a quantum mechanical solute computer simulation studies of the photoexcited hydrated electron, J.Chem.Phys., 101 (1994), 6902-6916... 

Alfano, J. C., Walhout, P. K., Kimura, Y. and Barbara, P. F. Ultrafast transient-absorption spectroscopy of the aqueous solvated electron, J.Chem.Phys., 98 (1993), 5996-5998... 

A pulse radiolysis study of the reaction between aqueous solvated electrons and benzyltrimethylammonium ions shows that dissociative electron transfer occurs to generate the benzyl radical, identified by uv-spectroscopy. No detectable intermediate is formed [40]. 

Storer etal. (1994) employed a SM.v GB continuum solvent model to investigate this question. Because of die efficiency of die continuum model, they were able to examine various levels of electronic-structure dieory in assessing the influence of aqueous solvation... 

Reid PJ, Silva C, Walhout PK, Barbara PE. (1994) Femtosecond absorption anisotropy of the aqueous solvated electron. Chem Phys Lett 228 658-664. 

Resonance Raman (RR) experiments have also provided valuable data on the structure of the electron. RR spectra of aqueous solvated electrons revealed enhancements of the water inter- and intra-molecular vibrations demonstrating that electronic excitation was significantly coupled to these modes. Frequency downshifts of the resonantly enhanced H2O bend and stretch were explained by charge donation into solvent frontier orbitals. RR spectra in primary alcohols (methanol, ethanol, propan-l-ol) revealed strong vibronic coupling of the solvated electron to at least five normal modes of the solvent. The spectra showed enhancements of the downshifted OH stretch. 

Tauber MJ, Mathies RA.. (2003) Structure of the aqueous solvated electron from Resonance Raman spectroscopy Lessons from isotopic mixtures, Chem Soc 125 1394-1402. 

As discussed earlier in the section on heterocyclic equilibria, heterocycles show large changes in electronic structure between the gas phase and solution, and thus the effects of aqueous solvation on nucleic acid bases is very interesting. 

Figure 3 presents a comparison of the non-equilibrium solvent response functions, Eq (1), for both the photoexcitation ("up") and non-adiabatic ("down") transitions (cf. Fig. 2). The two traces are markedly different the inertial component for the downwards transition is faster and accounts for a much larger total percentage of the total solvation response than that following photoexcitation. The solvent molecular motions underlying the upwards dynamics have been explored in detail in previous work, where it was also determined that the solvent response falls within the linear regime. Unfortunately, the relatively small amount of time the electron spends in the excited state prevents the calculation of the equilibrium excited state solvent response function due to poor statistics, leaving the matter of linear response for the downwards S(t) unresolved. Whether the radiationless transition obeys linear response or not, it is clear that the upward and downwards solvation response behave very differently, due in part to the very different equilibrium solvation structures of the ground and excited state species. Interestingly, the downwards S(t), with its much larger inertial component, resembles the aqueous solvation response computed in other simulation studies, and bears a striking similarity to that recently determined in experimental work based on a combination of depolarized Raman and optical Kerr effect data. ...

Non-aqueous Solvation.—Structural radii and electron-cloud radii, together with lattice enthalpies and enthalpies of solvation of ionic crystals, have been reviewed.84 The free energies of transfer, AGtr(K+), of potassium ions from water to 14 non-aqueous solvents have been reported, and they were derived from measurements in an electrochemical cell assumed to have a negligible liquid-junction potential. The essentially electrostatic nature of its solvation allows K+ to be used as a model for non-specific solvent-ion interactions. A... 

The other proposed mechanism involves the reduction of ground triplet state oxygen by an aqueous solvated electron generated by excited triplet state DOM [70-72] ... 

Recently, Thomas-Smith and Blough [73] determined that quantum yields for the production of the aqueous solvated electron in irradiated coastal DOM samples were too low to account for the production of 02 (as determined from the yield of H2O2), suggesting that reaction (3) is the main source of 02 in natural waters. 

M. J. Tauber and R. A. Mathies,/. Am. Chem. Soc., 125, 1394-1402 (2003). Structure of the Aqueous Solvated Electron from Resonance Raman Spectroscopy Lessons from Isotopic... 

The aqueous solvated electrons, Qf, and H atoms are strong reducing agents and were able to reduce metal ions down to the zero-valent state (Eq. 2 and 3)... 

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