[en] The use of pulse radiolysis to learn about processes which occur before the beginning of chemical times is discussed. Two examples, the distance distribution of positive and negative ions in hydrocarbons, and the state of the dry electron are discussed in detail

[en] In this paper we describe our measurements of ion solvation in a series of alcohols. Benzophenone is dissolved in an alcohol at a sufficiently high concentration so that the electrons formed by radiation will react with the benzophenone molecule to form the anion. The spectrum of the anion is then observed as a function of time. As the benzophenone anion solvates, the spectrum shifts to the blue. The results of our measurements clearly show that both the size of the solvent molecules and their shapes are important in the solvation process. Different spectral relaxation processes are observed for ions than are observed for electron solvation, the ''simple'' ion system that has been most heavily studied. In addition, these results suggest that the rate of solvation may be different for ions in solution than for dipoles in solution. 26 refs., 3 figs

[en] Gas phase pulse radiolysis, a technique which can be used to study many different phenomena in chemistry and physics, is discussed. As a source of small radicals, pulse radiolysis is important to the field of chemistry, particularly to combustion and atmospheric kinetics. The reactions of 1,3-butadiene, allene, ethylene and acetylene with OH are presented. 52 refs., 1 fig., 1 tab

[en] One uncertainty in the pre-chemical period is the travel of the electron prior to thermalization. It is shown that radiation chemistry, while unable to determine the distribution of ions, can act as a sensitive test for distributions. Chemical evolution in the pre-chemical times may also be inferred

[en] This is a response to Matsuzaki, Kobayashi, and Nagakura (MKN), that it is unlikely the electron has a solvation time of 55 ps in 6.2M NaOH. The reason for their results are not clear; however, they may be due to observing a different species than the hydrated electron. They do not know the identity of the species giving rise to the spectrum shown by MKN, but it is strikingly similar to that of the spectrum assigned to the B-naphthol singlet by Klanning. 2 figures

No abstract available

[en] The reaction of e^-/sub aq/ with HgCl₂, a neutral species, is diffusion-controlled. At high concentrations of solute the rate constant is time-dependent in accord with the Noyes' equation. The hydrated electron reacts with Ag⁺ in concentrated solutions of AgClO₄ without acquiring an ionic atmosphere, consequently diminishing the effect of ionic strength on the rate constant in pure AgClO₄ solutions. Although there is, therefore, presumably a small ionic strength effect for e^-/sub aq/ + Ag⁺ in pure AgClO₄ solutions, the rate constant still increases at high concentration (short times), again in accord with theory

No abstract available

[en] Spur decay kinetics of the hydrated electron following picosecond pulse radiolysis of water have been measured using a time-correlated transient absorption technique with an asynchronous mode-locked laser. The 11 ns time window afforded by this signal-averaging technique is ideal to match up with more conventional transient absorption measurements taken to microsecond time scales. The precise data recorded in this study require a revision downward of the time zero solvated electron yield to approximately 4.0 per 100 eV of energy absorbed, to match the best available scavenger product measurements

[en] A direct measurement of the geminate decay process between the electron and the positive ion in n-hexane and cyclohexane is presented. For n-hexane, the decay is that which has been predicted for geminate ion decay processes in which the distribution function for the distance between positive and negative ions is exponential. For cyclohexane, the decay is well described by an exponential process with a decay time of 0.58 ns. (author)