Subexcitation electrons thermalization

The molecular time scale may be taken to start at 10 14 s following energy absorption (see Sect. 2.2.3). At this time, H atoms begin to vibrate and most OH in water radiolysis is formed through the ion-molecule reaction H20+ + H20 H30+ + OH. Dissociation of excited and superexcited states, including delayed ionization, also should occur in this time scale. The subexcitation electron has not yet thermalized, but it should have established a quasi-stationary spectrum its mean energy is expected to be around a few tenths of an eV. 

In liquefied rare gases (LRG) the ejected electron has a long thermalization distance, because the subexcitation electrons can only be thermalized by elastic collisions, a very inefficient process predicated by the small mass ratio of the electron to that of the rare gas atom. Thus, even at a minimum of LET (for a -1-MeV electron), the thermalization distance exceeds the interionization distance on the track, determined by the LET and the W value, by an order of magnitude or more (Mozumder, 1995). Therefore, isolated spurs are never seen in LRG, and even at the minimum LET the track model is better described with a cylindrical symmetry. This matter is of great consequence to the theoretical understanding of free-ion yields in LRG (see Sect. 9.6). 

The subexcitation electrons lose their energy in small portions, which are spent on excitation of rovibrational states and in elastic collisions. In polar media there is an additional channel of energy losses, namely, the dipole relaxation of the medium. The rate with which the energy is lost in all these processes is several orders of magnitude smaller than the rate of ionizaton losses (see the estimates presented in Section II), so the thermalization of subexcitation electrons is a relatively slow process and lasts up to 10 13 s or more. By that time the fast chemical reactions, which may involve the slow electrons themselves (for example, the reactions with acceptors), are already in progress in the medium. For this reason, together with ions and excited molecules, the subexcitation electrons are active particles of the primary stage of radiolysis. 

In the problem of retardation of subexcitation electrons, the two important characteristics are the thermalization time and the thermalization path length. In condensed media the key role is played by thermalization path length, which determines how far can an electron travel away from its parent ion when it is thermalized. The thermalization path length determines the probability of formation of a free ion. 

The thermalization path length of subexcitation electrons has been the object of many discussions from the time the first track models appeared up to this day. The reason is that for quite a long time there were no direct methods of measuring the path lengths of slow electrons, while the corresponding theoretical analysis is very difficult owing to the need to take into account all the processes relevant to retardation of subexcitation electrons. 

Samuel and Magee250 were apparently the first to estimate the path length /th and time rth of thermalization of slow electrons. For this purpose they used the classical model of random walks of an electron in a Coulomb field of the parent ion. They assumed that the electron travels the same distance / between each two subsequent collisions and that in each of them it loses the same portion of energy A E. Under such assumptions, for electrons with energy 15 eV and for AE between 0.025 and 0.05 eV, they have obtained Tth 2.83 x 10 14 s and /th = 1.2-1.8 nm. At such short /th a subexcitation electron cannot escape the attraction of the parent ion and in about 10 13 s must be captured by the ion, which results in formation of a neutral molecule in a highly excited state, which later may experience dissociation. However, the experimental data on the yield of free ions indicated that a certain part of electrons nevertheless gets away from the ion far enough to escape recombination. 

So, as one can see, this method of determining the thermalization path length is not straightforward and involves many assumptions and suppositions. First, the value of r0 depends on the specific choice of the function F r) (see, e.g., Ref. 269) and is too uncertain to enable us to determine the processes that are responsible for retardation of subexcitation electrons in a medium (see the discussion in Ref. 271). However, by comparing the values of r0 for different substances we are able to determine some of the factors that affect the path length of slow electrons. Since the value of r0 depends on the density p of the liquid, it is reasonable to compare the products prQ rather than the values of r0 themselves. 

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