Optical spectrum, pulse radiolysis

Asmus et al. unambiguously identified a variety of [R2S.. SR2] radical cations in solution and measured their optical absorption spectra using pulse radiolysis techniques [133]. They proposed that the spectrum of [H2S. .SH2] arises from the transition in the three-electron S.. S... 

Let us consider the data on the dependence of the kinetics of et decay at 77 K on the radiation dose. As seen from Fig. 11, over the dose range 3 x 1019 - 3.6 x 102° eV cm 3, the kinetics of et decay is virtually independent of the dose. At the same time, at lower doses, the decay of et is significantly slowed down. For example, for a dose of 1019 eV cm-3, the change in optical density of y-irradiated samples at the maximum (585 nm) of the et absorption spectrum with time is also described by eqn. (5), but the slope of the kinetic curve the coefficient M in eqn. (5)] is smaller by almost a factor of two [28] than for the curve of Fig. 11. Further investigations by pulse radiolysis technique with spectrophotometric recording of et showed that, at a still lower dose (6 x 1017 eV cm"3) no decay of et in water-alkaline matrices is observed at all [43] while at high doses (5 x 1021 eV cm"3) for the same samples, the decay of efr does occur [43]. A decrease in the rate of etr decay via the reaction with O at small doses was also reported in ref. 44. This behaviour of the kinetic curves seems to reflect special features of the spatial distribution of etr and 0 particles in samples irradiated with different doses. 

The solvated electron has been studied in a number of organic liquids, among which are the aliphatic alcohols (27, 28, 3, 2d, 2, 27), some ethers (25, 5), and certain amines (9, 22, 2). Of these systems, it is only in the alcohols, to which this paper is principally but not exclusively directed, that both the chemical reactivity and the optical absorption spectrum of the solvated electron have been investigated in detail. The method used in these studies is that of pulse radiolysis (22, 22), developed some five years ago. The way was shown for such investigations of the solvated electron by the observation of the absorption spectrum of the hydrated electron (6, 28, 19) and by the subsequent kinetic studies (2d, 22, 20) which are being discussed in other papers in this symposium. 

Finally, the development of pulse radiolysis enabled a direct observation of e aq, and a direct distinction between e aq and H could easily be made. Matheson (37) (with spectroscopic data obtained by Keene) suggested that e ag has optical absorption in the visible. Hart and Boag (26) used spectrographic plates and studied this absorption. The effect of solutes, which were known as electron scavengers led to the conclusion that the absorption was due to e aq. It was confirmed later, that the absorption belonged to unit negatively charged species by means of a salt effect (20), as well as by conductivity measurements (49). Many more papers on the absorption spectrum and rate constants of the hydrated electron have since appeared (16). 

Weeks, J.L. and Rabani, J., The pulse radiolysis of deaerated aqueous carbonate solutions. I Transient optical spectrum and mechanism II pK for OH radicals, J. Phys. Chem., 70(7), 2100-2106, 1966. 

While the study of solvatochromic dyes is well established as a means of probing solvent polarity, these are not the only solutes that can be used in this fashion. A more exotic solvatochromic probe is an excess electron in solution. Optical absorption studies of the thermalized (solvated) electron generated in the pulse radiolysis of a series of ILs show a strong dependence on cation character, with a relatively low frequency for tetraalkylammonium systems and a higher frequency for cyclic (pyrrolidinium-based) cations [48, 207]. The solvated electron spectrum is often interpreted in a particle-in-a-box framework, which would imply that the cyclic cations (which possess smaller ionic volumes) simply coordinate more closely with the electron and so create a smaller domain in which the electron must localize. The breadth of the absorptions and their maximum fall within the range of values expected for moderately polar organic solvents. 

However, this mechanism does not explain the chain reaction. Tabata and coworkers measured the optical spectrum of the dimer cation radical, by pulse radiolysis of benzonitrile solution of the dimer immediately after the pulse. They found only a peak at 770 nm without other peaks, except for a possible small shoulder at 740 nm (which is within the limit of experimental error). Addition of cation scavengers leads to elimination of this spectrum, while oxygen does not remove it, suggesting that the spectrum is due to a cation. This 770-nm peak of the cation of the cyclodimer of VC reminds one of the 770-nm peak found 1.6 jus after the pulse in the case of 1 M VC solution. It should be noticed that while in this second paper the authors also mentioned this shift from 790 nm to 770 nm, the data in their figure show a peak at 790 nm both immediately and 1.6 jus after the pulse. Consequently, Tabata and coworkers suggested that the observed spectrum in pulse radiolysis of aerated solution of VC in benzonitrile is a composite of the spectrum of VC cation together with that of the cation of the cyclodimer of VC. The contribution of each intermediate to the observed spectrum depends on the concentration of VC and how long after the pulse the spectrum was taken. In a dilute solution, the dimer cation will be produced as time proceeds, but it is absent immediately after the pulse. In concentrated solutions, both cations coexist even immediately after a pulse. 

In solid-state studies, ESR spectroscopy is the best detection method for studying radical intermediates in radiolysis. It is, however, difficult to apply to liquid-phase studies, and generally, optical methods are favoured. In solid-state work, radicals are trapped (matrix-isolated) and can be studied by any spectroscopic technique at leisure. However, for liquid-phase studies, time-resolved methods are often necessary because the intermediates are usually very short lived. In the technique of pulse radiolysis, short pulses of radiation, followed by pulses of light which explore the UV spectrum, are used. The spectra help to identify the species, but also their kinetic behaviour can be accurately monitored over very short time-scales (from picoseconds to milliseconds). This technique is discussed in Section 3.3. 

The electrons ejected from molecules by the passage of ionizing radiation through condensed media can be solvated very soon after the primary ionizing event and the solvated electron, e q, so formed can undergo chemical reactions with solute and solvent molecules. The main evidence for the existence of solvated electrons in the liquid phase has been obtained by the use of pulse radiolysis in conjunction with optical spectroscopy (Hart and Boag, 1962). Very recently the e.s.r. spectrum of the solvated electron has been obtained by a similar method (Avery et ah, 1968). The solvated electron is not located on one solvent molecule but is associated with an assembly of molecules which form a potential well around the electron by virtue of dipolar and polarization forces. There is a close similarity between this system and the blue solutions obtained by dissolving alkali metals in liquid ammonia. 

Early work (21,22) on the absorption spectrum of the ascorbate radical failed to take into account the complex nature of the reaction between ascorbate and the OH radical, which was later shown by ESR studies (18,19) and by optical pulse radiolysis using very short pulses (23). 

See reviews a) Edwards P.R, The electronic properties of metal solutions in liquid ammonia and related solvents, Adv. Inorg. Chem. Radiochem., i982,25, 135-185. b) Boag J.W., Pulse radiolysis a historical account of the discovery of the optical absorption spectrum of the hydrated electron, in Early developments in radiation chemistry", KrohJ. (Ed.), Royal Society ofChemistry, Cambridge, 1989, 7-20. 

A major characteristic of the solvated electron is its optical absorption spectrum. The optical absorption spectrum ofthe hydrated electron was first determined in 1962 by Hart and Boag using transient absorption measurements in pulse radiolysis of pure water and aqueous solutions of carbonates it appears as an intense broad structureless band with a maximum around 720 nm in pure water [1 j.Then, optical absorption spectra were reported for the solvated electron in a large number of solvents. The position ofthe maximum and the width ofthe absorption band depend on the medium. Figure 2 shows the optical absorption spectrum of the solvated electron in various solvents at room temperature. The solvents may be classified in three groups ... 

Such reduction reactions have been observed directly by pulse radiolysis for several metal ions. Most ofthe reduction steps have been observed and their rate constants determined. Figure 1 presents the example of Ag reduction observed by pulse radiolysis coupled with time-resolved spectrophotometry. The evolution of the optical absorption spectrum in the successive fast steps is recorded just before and after the short electron pulse delivering the irradiation dose, as in a movie filming the fast cascade of reactions initiated... 

---