Temperature and isotope effects on the shape of the optical absorption spectrum of solvated electrons in water

1979 ◽  
Vol 83 (18) ◽  
pp. 2383-2387 ◽  
Author(s):  
Fang-Yuan. Jou ◽  
Gordon R. Freeman
1998 ◽  
Vol 76 (4) ◽  
pp. 411-413
Author(s):  
Yixing Zhao ◽  
Gordon R Freeman

The energy and asymmetry of the optical absorption spectrum of solvated electrons, es- , change in a nonlinear fashion on changing the solvent through the series HOH, CH3OH, CH3CH3OH, (CH3)2CHOH, (CH3)3COH. The ultimate, quantum-statistical mechanical, interpretation of solvated electron spectra is needed to describe the solvent dependence. The previously reported optical spectrum of es- in tert-butanol was somewhat inaccurate, due to a small amount of water in the alcohol and to limitations of the infrared light detector. The present note records the remeasured spectrum and its temperature dependence. The value of the energy at the absorption maximum (EAmax) is 155 zJ (0.97 eV) at 299 K and 112 zJ (0.70 eV) at 338 K; the corresponding values of G epsilon max (10-22 m2 aJ-1) are 1.06 and 0.74. These unusually large changes are attributed to the abnormally rapid decrease of dielectric permittivity of tert-butanol with increasing temperature. The band asymmetry at 299 K is Wb/Wr = 1.8.Key words: optical absorption spectrum, solvated electron, solvent effects, tert-butanol, temperature dependence.


Author(s):  
P. Krebs

Some years ago Jay-Gerin and Ferradini attempted to establish a correlation between the optical absorption spectrum and the mobility of excess electrons in various polar solvents (J. Chem. Phys.


1971 ◽  
Vol 49 (20) ◽  
pp. 3398-3401 ◽  
Author(s):  
D. C. Walker ◽  
S. C. Wallace

From the optical absorption spectrum observed by a sub-nanosecond pulse radiolysis method it is concluded that irradiated pure liquid formamide (dielectric constant = 109) does not yield solvated electrons with lifetimes >10−11 s. In formamide–water mixtures the hydrated electron is formed in low yield and the position of the absorption band of eaq− is not altered by changing the composition. Apparently formamide reacts much more rapidly with thermalized electrons than it does with hydrated electrons. The latter may be formed in formamide–water mixtures due to aggregates of water molecules.


2016 ◽  
Vol 109 (26) ◽  
pp. 263104 ◽  
Author(s):  
Baomin Wang ◽  
Xuewei Cao ◽  
Zhan Wang ◽  
Yong Wang ◽  
Kaihui Liu

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