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In this study, we use Monte Carlo track chemistry simulations to show that 'dry' secondary electrons, precursors of the 'hydrated' electron ([e.sup.-.sub.aq]), can be scavenged on the sub-picosecond time scale prior to hydration, by a high concentration (>0.1-1M) of azide ions ([N.sub.3.sup.-])in water irradiated with [.sup.60]Co [gamma]-rays and tritium [beta]-electrons at 25 [degrees]C. This is a striking result, as [N.sub.3.sup.-] is known to react very slowly with [e.sup.-.sub.aq]. These processes tend to significantly reduce the yields of [H.sub.2] as observed experimentally. For both energetic Compton electrons ('linear energy transfer', LET ~ 0.3 keV/[micro]m), which are generated by the cobalt-60 [gamma]-rays, and [.sup.3]H [beta]-electrons (LET ~ 6keV/[micro]m), our [H.sub.2] yield results confirm previous Monte Carlo simulations, which indicated the necessity of including the capture of the precursors to [e.sup.-.sub.aq]. Interestingly, our calculations show no significant changes in the scavenging of 'dry' electrons at high azide concentrations in passing from [gamma]-radiolysis to tritium [beta]-radiolysis (i.e., with LET). This led us to the conclusion that the higher [H.sub.2] yield observed experimentally for [.sup.3]H [beta]-electrons compared with [.sup.60]Co [gamma]-rays is mainly explained by the difference in the radiation track structures during the chemical stage (>1 ps). The higher LET of tritium [beta]-electrons leads to more molecular products ([H.sub.2] in this case) in tritium radiolysis than in [gamma]-radiolysis. Finally, a value of ~0.5 nm was derived for the reaction distance between [N.sub.3.sup.-] and the 'dry' electron from the [H.sub.2] yields observed in [.sup.60]Co [gamma]-radiolysis at high [N.sub.3.sup.-] concentrations. Key words: liquid water, azide ion ([N.sub.3.sup.-]) solutions, radiolysis, linear energy transfer (LET), cobalt [gamma]-rays, tritium [beta]-electrons, secondary electrons, 'dry' electron scavenger, mobility, [H.sub.2] yield, Monte Carlo track chemistry simulations. Dans le cadre de la presente etude, nous avons utilise des simulations Monte Carlo de la trajectoire des particules pour montrer que les electrons secondaires dits << secs >>, precurseurs des electrons << hydrates >> ([e.sup.-.sub.aq]), peuvent etre pieges, a une echelle de tempssousla barriere de la picoseconde avant l'hydratation, par des ions azoture ([N.sub.3.sup.-]) a forte concentration (>0,1 a 1 M) dans l'eau soumise a l'irradiation par des rayons [gamma] de [.sup.60]Co et des electrons [beta] de tritium a 25 [degrees]C. Ce resultat est etonnant, puisque l'on sait que [N.sub.3.sup.-] reagit tres lentement avec les [e.sup.-.sub.aq]. Ces processus ont tendance a reduire de facon considerable les rendements en [H.sub.2], comme cela est observe experimentalement. Pour les electrons Compton de haute energie (transfert d'energie lineaire [TEL] ~ 0,3 keV/[micro]m), qui sont generes par les rayons [gamma] du cobalt 60, et les electrons [beta] du [.sup.3]H (TEL ~ 6keV/[micro]m), nos resultats du rendement en [H.sub.2] confirment les simulations Monte Carlo precedentes, qui ont indique la necessite d'inclure le piegeage des precurseurs des [e.sup.-.sub.aq]. Fait interessant, lorsque l'on passe de la radiolyse [gamma] a la radiolyse [beta] par le tritium, nos calculs ne montrent aucun changement substantiel quant au piegeage des electrons << secs >> a des concentrations elevees d'azoture. Ces resultats nous amenent a conclure que le rendement plus eleve en [H.sub.2] observe experimentalement pour les electrons [beta] du [.sup.3]H par rapport aux rayons [gamma] du [.sup.60]Co s'explique principalement par la difference entre la structure des trajectoires de rayonnement pendant le stade chimique (>1 ps). Le TEL plus eleve des electrons [beta] du tritium donne lieu a la formation d'un plus grand nombre de produits moleculaires ([H.sub.2] dans ce cas) lors de la radiolyse par le tritium que lors de la radiolyse [gamma]. Enfin, nous avons calcule une valeur d'environ 0,5 nm pour ce qui est de la distance de reaction entre [N.sub.3.sup.-] et l'electron << sec >> a partir des rendements en [H.sub.2] observes lors de la radiolyse [gamma] par le [.sup.60]Co a des concentrations elevees de [N.sub.3.sup.-]. [Traduit par la Redaction] Mots-cles : eau liquide, solutions d'ions azoture ([N.sub.3.sup.-]), radiolyse, transfert d'energie lineaire (TEL), rayons [gamma] de cobalt, electrons [beta] de tritium, electrons secondaires, piegeur d'electrons << secs >>, mobilite, rendement en [H.sub.2], simulations Monte Carlo de la trajectoire des particules., 1. Introduction The radiation chemistry of liquid water (1-3) is of fundamental importance for a variety of practical applications, particularly in the nuclear power industry, where radiolysis products cause corrosion [...]

The flexible waste management (FWM) system has been proposed in order to apply the partitioning and transmutation (P&T) technology for minor actinides (MA) to the current high-level liquid waste (HLLW). This system consists of HLLW calcination to produce easy-to-dissolve granule; its temporary storage is required until the P&T technology deployment and re-dissolution of the granule to remove MA from HLLW after the future P&T technology deployment. The fundamental experiments were conducted to clarify the applicability of FWM system to the current HLLW, and the results indicate the technological validity of the system. The evaluations were carried out for the reduction of storage amount, potential radiotoxicity, and repository area of high-level waste. [ABSTRACT FROM AUTHOR]

Reduced graphene oxide (rGO) composite aerogels were synthesized by the radiation reduction of graphene oxide (GO) with the assistance of Eu3+, which demonstrated excellent adsorption performance for diverse organic pollutants. Eu3+ promoted the formation of the gel by inducing the pre-assembly of GO so that the required pH range for synthesizing the rGO aerogel by radiation reduction was broadened and the minimum absorbed dose was also reduced. At pH 2, the Eu3+-induced pre-assembly fabricated more mesopores and enlarged the specific surface area of the obtained hierarchically porous rGO-Eu composite aerogel, which enabled the high-capacity (81–395 g g−1) and ultrafast removal of organic solvents. The different effects of organic solvents on the unique fluorescence emission of Eu(III) also allowed the in situ detection of certain organic solvents such as pyridine. At pH 6, Eu3+ enhanced the reduction of GO by capturing more hydrated electrons, the most reductive species produced by water radiolysis, and synergistically reduced GO. The obtained rGO-Eu composite aerogel with a high reduction degree, demonstrated outstanding adsorption capacities for various anionic organic dyes (40.5–1572.5 mg g−1) owing to the strong π–π interaction and electrostatic attraction. Benefitting from high reduction, it demonstrated adsorption capacity for cationic dyes (97.3–1367.6 mg g−1) comparable to other reported graphene-based aerogels. The rGO-Eu aerogel prepared by radiation reduction might be suitable as a broad-spectrum adsorbent for organic pollutants. [ABSTRACT FROM AUTHOR]

Metal oxide nanocluster resists are a promising candidate for enabling the high-volume production of semiconductor devices with high-numerical-aperture extreme ultraviolet exposure tools. In this study, the sensitization mechanism of metal oxide nanocluster resists was investigated by focusing on the radiation-induced reactions of carboxylic acid ligands. Radiolytic products in various solutions of unsaturated carboxylic acids, aromatic carboxylic acids, and saturated carboxylic acids were analyzed by electrospray ionization mass spectrometry, high-performance liquid chromatography, and dynamic light scattering. The conditions of the solutions were selected to control reaction paths of intermediates. The major reaction paths induced by ionizing radiation were clarified. The obtained results suggest that the generation of bridging ligands is essential to the sensitization of metal oxide nanocluster resists. Both low-energy electrons and radical cations can trigger dimerization. The diffusion of small radicals should be suppressed to prevent dimerization at undesired places. [ABSTRACT FROM AUTHOR]

The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiCl[O.sub.4] deuterated water solutions were measured by pulse radiolysis techniques from room temperature to 300 degree Celsius at a constant pressure of 25 MPa. The results indicated that when the temperature is increased and the density is decreased, the absorption spectrum of the electron in the presence of a lithium cation is shifted to lower energies.

Methyl viologen (1,1-dimethyl-4-4-bipyridinium dichloride) is used as a scavenger to estimate the radiolytic yields of water decomposition products from room temperature to 400 degree Celsius by pulse radiolysis method. {G(e(sub aq)(super -) + G(OH) + G(H)} is studied using a 0.5 mM MV(super 2+) solution in the presence of 10 mM NaCOOH up to 200 degree Celsius and in the presence of 0.2 M ethanol up to 400 degree Celsius.

Metal oxide nanocluster resists have recently attracted considerable attention for use in extreme ultraviolet lithography. To obtain sophisticated guidelines for material design, it is necessary to understand well the radiation-induced chemical reaction scheme including the insolubilization mechanism. In this study, the production of CO2, which is considered to be one of the end products of treatment with an ionizing radiation, was investigated for eight types of carboxylic acid under various conditions using γ-rays (60Co) as a radiation source. The amount of CO2 produced was measured by gas chromatography. GCO2 (/100 eV), which indicates decarboxylation efficiency, was evaluated. CO2 was generated through electron addition, hole transfer, and hydroxyl radical addition to the molecular and ionic forms of carboxylic acids. The dependences of GCO2 on reaction partners were clarified. The dependences of GCO2 on the molecular structure and dissociative state of carboxylic acids were also clarified. [ABSTRACT FROM AUTHOR]

A re-examination of our Monte-Carlo modeling of the radiolysis of liquid water by low linear-energy-transfer (LET ~ 0.3 keV [micro][m.sup.-1]) radiation is undertaken herein in an attempt to reconcile the results of our simulation code with recently revised experimental hydrated electron ([e.sup.-.sub.aq]) 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 [e.sup.-.sub.aq] yield of 4.0 [+ or -] 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 [e.sup.-.sub.aq] decay kinetic profile from 100 ps to 10 ns, and (iii) the time-dependent yields of the other radiolytic species H*, *OH, [H.sub.2], and [H.sub.2][O.sub.2] (up to ~1 [micro]s). The lowest possible limiting "time-zero" yield of [e.sup.-.sub.aq] 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 electron-cation recombination probability, averaged over the subexcitation electron "entry spectrum," are found to be equal to ~139 [Angstrom] and ~18%, respectively. These values are to be compared with those obtained in our previous simulations of liquid water radiolysis, namely ~88 [Angstrom] and ~5.5%, respectively. Our average electron thermalization distance is also to be compared with the typical size (~64-80 [Angstrom]) of the initial hydrated electron distributions estimated in current deterministic models of "spur" chemistry. Finally, our average probability for geminate electron-cation 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 [e.sup.-.sub.aq] yields at very short times are needed. Key words: liquid water, radiolysis, electron-cation geminate recombination, electron thermalization distance, hydrated electron ([e.sup.-.sub.aq]), [e.sup.-.sub.aq] decay kinetics, time-dependent molecular and radical yields, Monte-Carlo simulations.

The temperature dependence of the absorption spectrum of the formation and decay of dimer anion (SCN)(sub 2)(super dot-) is analysed in the temperature range of 25 to 400 degree Celsius. Analysis showed that the absorption peak shift to longer wavelength (red shift) with increase in temperature.

The radical yields in the aqueous solutions of thiocynate and methyl viologen (MV2+) produced due to radiolysis of water are measured by using proton pulses of 5.2 MeV energy. The amount of yield obtained suggest that the predicted OH radical yields for proton beams in both sets of solution increase with increasing scavenging capacity and approach the value found for high-energy electron radiolysis.

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Metal oxide nanocluster resists have recently attracted considerable attention for use in extreme ultraviolet lithography. In this study, radiation-induced reactions of carboxylic acids used as the ligands of metal oxide nanocluster resists were investigated using a pulse radiolysis method. Upon the irradiation of the aqueous solutions of calboxylic acids with an electron beam, radical dianions of carboxylates were generated under the basic condition. From the comparison between pulse radiolyses under acidic and basic conditions, the kinetics of the radical dianions was clarified. For aromatic carboxylates, anion radicals of carboxylic acids were generated through the reaction of their dianions with H2O. For unsaturated carboxylates, their radicals were generated through the reaction of their radical dianions with H2O. The carboxylic anions and vinyl groups were protonated for dianions of aromatic and unsaturated carboxylates, respectively. The proton dynamics control is important for the stable performance of metal oxide nanocluster resists. [ABSTRACT FROM AUTHOR]

The optical absorption spectra of the hydrated electron (eaq-) in supercritical (heavy) water (SCW) are measured by electron pulse radiolysis techniques as a function of water density at three temperatures of 380, 390, and 400 °C, and over the density range of ∼0.2–0.65 g/cm3. In agreement with previous work, the position of the eaq- absorption maximum (EAmax) is found to shift slightly to lower energies (spectral “redshift”) with decreasing density. A comparison of the present EAmax-density data with other measurements already reported in the literature in subcritical (350 °C) and supercritical (375 °C) water reveals that at a fixed pressure, EAmax decreases monotonically with increasing temperature in passing through the phase transition at tc. By contrast, at constant density, EAmax exhibits a minimum as the water passes above the critical point into SCW. These behaviors are explained in terms of simple microscopic arguments based on the crucial role played by local density and configurational fluctuations (associated with criticality) in providing pre-existing polymeric clusters, which act as trapping sites for electrons. [ABSTRACT FROM AUTHOR]