Electronic spectra of trapping electrons in .gamma.-irradiated organic-mixture glasses at 77.deg.K

Ito, T.; Ujikawa, N.; Fueki, Kenji

doi:10.1021/j100590a007

Cited by 11 publications

(2 citation statements)

References 3 publications

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“…The absorption spectrum of solvated electrons in a binary solvent exhibits a single absorption band with a maximum at an energy EAmax that is intermediate to the values of EAmax in the pure components (6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20). In a mixed solvent such as an alkane and an alcohol the electrons are selectively solvated by the alcohol (10)(11)(12)(13)(14)(15)(16).…”

Section: Introductionmentioning

confidence: 99%

“…In a mixed solvent such as an alkane and an alcohol the electrons are selectively solvated by the alcohol (10)(11)(12)(13)(14)(15)(16). Similarly, in mixtures of amines and alcohols (15), or an ether with an alcohol or water (17)(18)(19)(20), the electrons are selectively solvated by the more polar solvent. The degree of selective solvation is assessed by the relative position of EAmax between those for electrons in the pure components, compared to the composition of the solvent.…”

Section: Introductionmentioning

confidence: 99%

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Composition effects on optical absorption spectra of solvated electrons in alcohol/water mixed solvents

Leu¹,

Jha²,

Freeman³

1982

Can. J. Chem.

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AH-DONG LEU, KAMAL N. JHA, and GORDON R. FREEMAN. Can. J. Chem. 60,2342 (1982. Addition of a few percent of water to an alcohol has a relatively large effect on the shape of the optical absorption spectrum of solvated electrons in the liquid. This occurs whether the optical absorption energy in the pure alcohol is greater or smaller than that in water. Addition of up to 10mol% of water causes E,,,, in methanol and primary alcohols to decrease, while it increases in secondary and tertiary alcohols. At around 10mol% water in primary alcohols E,,,, passes through a minimum and increases again at higher water concentrations, reaching a plateau at about 30 mol% and remaining constant up to about 95 rnol% water; over the last part of the composition range to pure water E,,,, decreases slightly. The behavior in secondary and tertiary alcohols containing >30mol% water is similar to that in primary alcohols. The width of the band at half height W,,, is divided at E,,,, into "red side" and "blue side" portions W, and Wb, respectively. In methanol and in primary and secondary alcohols, addition of up to 30 mol% of water greatly reduces Wb but has relatively little effect on W,. At >30 mol% water Wb and W, are similar to those in pure water. In tertiary butyl alcohol the band width is similar to that in pure water, so addition of water to the alcohol makes little change in the band width. The waterlalcohol composition effects on the e; absorption band parameters are attributed to changes in solvent structure. This is especially evidenced by the minimum in E,,,, at 10 mol% water in a primary alcohol. The changes in band asymmetry Wb/ W, indicate that the types of electronic transition on the low and high energy sides of the band are different. Introduction structure. Simons and co-workers have formulated The energy levels of solvated electrons, as the problem (3, 4), appropriately introducing the reflected in the energy of the optical absorption effects of fluct~ations in solvent properties at an maximum EAmax, are determined more by details of early stage of the model. Ultimately it was not the liquid structure than by the dielectric constant possible to use realistic Structure properties in the or the molecular dipole moment (l,2). The breadth ~alcdations-For example, the orientational

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