Theoretical calculations of pulse radiolysis spectra of trapped electrons in glassy media

1986 ◽  
Vol 101 (2) ◽  
pp. 257-265 ◽  
Author(s):  
D. Światła ◽  
W. M. Bartczak ◽  
J. Kroh
Keyword(s):  
Pulse Radiolysis ◽  
Theoretical Calculations ◽  
Trapped Electrons ◽  
Glassy Media

Structures of 4-substituted thioanisole radical cations studied by time-resolved resonance Raman spectroscopy during pulse radiolysis and theoretical calculations

RSC Advances ◽  
2016 ◽  
Vol 6 (111) ◽  
pp. 109334-109339 ◽  
Author(s):  
Sachiko Tojo ◽  
Mamoru Fujitsuka ◽  
Tetsuro Majima
Keyword(s):  
Raman Spectroscopy ◽  
Pulse Radiolysis ◽  
Dft Calculation ◽  
Theoretical Calculations ◽  
Resonance Raman Spectroscopy ◽  
Resonance Raman ◽  
Radical Cations ◽  
Time Resolved ◽  
Spin Distributions

The structures of 4-substituted thioanisole radical cations were studied by time-resolved resonance Raman spectroscopy during pulse radiolysis and DFT calculation, indicating importance of charge and spin distributions toward the dimerization.

A study of trapped electrons in LiCl/D2O and other aqueous glasses at temperatures down to 2 K by radiolysis, pulse radiolysis, photolysis, and stimulated luminescence

1979 ◽  
Vol 57 (12) ◽  
pp. 1488-1499 ◽  
Author(s):  
Norman V. Klassen ◽  
George G. Teather ◽  
Fernand Kieffer
Keyword(s):  
Absorption Spectrum ◽  
Decay Rate ◽  
Pulse Radiolysis ◽  
Trapped Electrons ◽  
Initial Yield ◽  
Free Transition

Pulse radiolysis of 9.5 M LiCl/D2O glass at 6 K produces both types of trapped electrons, evis− and eir−, just as it does at 75 K. However, going from 75 K to 6 K increases the initial yield of eir− and decreases its decay rate, while the yield of evis− decreases and its decay rate increases. These results are attributed to fast trap-to-trap tunnelling of evis− from unrelaxed traps at 6 K and slower tunnelling from deeper traps at 75 K while the eir− traps seem to relax within 100 ns even at 6 K. In 12 M LiCl/D2O at 4–10 K the initial evis− band with λmax = 625 nm decays considerably over minutes revealing a stable band with λmax = 695 nm. The stimulation spectrum and absorption spectrum of this stable band indicate a bound–free transition of 2.0 eV and a bound–bound transition of 1.8 eV. Similar measurements of evis− at 77 K indicate a bound–free transition of 2.6 eV and a bound–bound transition of 2.1 eV. Tryptophan was photolyzed in 9.5 M LiCl/D2O at 2 K to produce eir−.

A pulse radiolysis study of trapped electrons in aqueous ethylene glycol glasses

1983 ◽  
Vol 61 (1) ◽  
pp. 189-193 ◽  
Author(s):  
Zhennan Wu ◽  
Norman V. Klassen ◽  
Hugh A. Gillis ◽  
George G. Teather
Keyword(s):  
Ethylene Glycol ◽  
Reaction Kinetics ◽  
Pulse Radiolysis ◽  
Trapped Electrons ◽  
Aqueous Ethylene Glycol ◽  
The Stability ◽  
Kinetics Of

The yield and reaction kinetics of trapped electrons, [Formula: see text] and [Formula: see text], in several ethylene glycol/D2O glasses have been studied from 6–72 K by pulse radiolysis. An increased D2O concentration is believed to increase the concentration of IR-traps thereby leading to a greater [Formula: see text] and to decrease the concentration of VIS-traps thereby increasing the stability of [Formula: see text]. The yield and stability of [Formula: see text] are also increased by lowering the temperature. A redetermination of [Formula: see text] (1.3 × 104 M−1 cm−1 at 1800 nm) confirms earlier values.

Pulse radiolysis of deuterated aqueous LiCl glasses. Dependence of the yields and rates of reaction of visible and infrared absorbing trapped electrons on LiCl concentration

1978 ◽  
Vol 56 (14) ◽  
pp. 1889-1897 ◽  
Author(s):  
Hugh A. Gillis ◽  
George G. Teather ◽  
George V. Buxton
Keyword(s):  
Low Temperatures ◽  
Pulse Radiolysis ◽  
Hydration Number ◽  
Water Environment ◽  
Trapped Electrons ◽  
Straight Line Passing ◽  
Straight Line ◽  
Rate Of Reaction ◽  
Line Passing ◽  
The Difference

The yields and reactions of trapped electrons which absorb in the visible (evis−) and infrared (eir−) have been studied by pulse radiolysis in deuterated aqueous 6–15 M LiCl glasses at low temperatures. At 76 K G(evis−) increases and G(eir−) decreases as the concentration of LiCl is increased, but [Formula: see text] over the whole concentration range. Because the hydration number of Li+ is 4, G(eir−)/G(evis−) was plotted against [free D2O]/[LiCl•4D2O] and found to give a straight line passing through the origin, for [D2O]/[LiCl] > 4. From this proportionality it is concluded that eir− is an electron trapped in a purely amorphous water environment and evis− is mainly associated with water bound to Li+.The reactions of eir− and evis− with Cu(II) and SeO42− have been investigated. At 138 K the rate of reaction of evis− with SeO42− increases with decreasing [LiCl] whereas its rate of reaction with Cu(Il) is slower and independent of [LiCl]. At 76 K, where the rates of reaction of eir− with the scavengers can also be measured, it is found that in each case evis− and eir− react more slowly in 12 M LiCl glass than in 6 M LiCl glass, the difference being more marked for SeO42−. In the absence of scavenger the electron in the smaller yield decays faster. These observations can be rationalized on the basis that electrons can tunnel in either direction between visible and infrared traps before being scavenged, and it seems they cannot be rationalized in terms of direct tunnelling only.G(Cl2−) is found to be proportional to the electron fraction of Cl−•3D2O in the glass and its extrapolated value for pure Cl−•3D2O is 3.4. It is inferred that Cl2− arises mainly from ionization of the D2O bound to Cl−.

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