A re-examination of our Monte-Carlo modeling of the radiolysis of liquid water by low linear-energy-transfer (LET ~ 0.3 keV µm1) radiation is undertaken herein in an attempt to reconcile the results of our simulation code with recently revised experimental hydrated electron (eaq) yield data at early times. The thermalization distance of subexcitation electrons, the recombination cross section of the electrons with their water parent cations prior to thermalization, and the branching ratios of the different competing mechanisms in the dissociative decay of vibrationally excited states of water molecules were taken as adjustable parameters in our simulations. Using a global-fit procedure, we have been unable to find a set of values for those parameters to simultaneously reproduce (i) the revised eaq yield of 4.0 ± 0.2 molecules per 100 eV at "time zero" (that is, a reduction of ~20% over the hitherto accepted value of 4.8 molecules per 100 eV), (ii) the newly measured eaq decay kinetic profile from 100 ps to 10 ns, and (iii) the time-dependent yields of the other radiolytic species H, OH, H2, and H2O2 (up to ~1 µs). The lowest possible limiting "time-zero" yield of eaq that we could in fact obtain, while ensuring an acceptable agreement between all computed and experimental yields, was ~4.4 to 4.5 molecules per 100 eV. Under these conditions, the mean values of the electron thermalization distance and of the geminate electroncation recombination probability, averaged over the subexcitation electron "entry spectrum," are found to be equal to ~139 Å and ~18%, respectively. These values are to be compared with those obtained in our previous simulations of liquid water radiolysis, namely ~88 Å and ~5.5%, respectively. Our average electron thermalization distance is also to be compared with the typical size (~6480 Å) of the initial hydrated electron distributions estimated in current deterministic models of "spur" chemistry. Finally, our average probability for geminate electroncation recombination agrees well with an estimated value of ~15% recently reported in the literature. In conclusion, this work shows that an adaptation of our calculations to a lower hydrated electron yield at early times is possible, but also suggests that the topic is not closed. Further measurements of the eaq yields at very short times are needed. Key words: liquid water, radiolysis, electroncation geminate recombination, electron thermalization distance, hydrated electron (eaq), eaq decay kinetics, time-dependent molecular and radical yields, Monte-Carlo simulations.
Sense amplifier offset voltage analysis for both time-zero and time-dependent variability