Absorption spectrum, yield, and decay kinetics of the solvated electron in pulse radiolysis of liquid ammonia at various temperatures

Farhataziz,; Perkey, Lewis M.

doi:10.1021/j100583a008

Cited by 24 publications

(10 citation statements)

References 3 publications

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“…This M-' cm-'. value is identical to that observed in aqueous The oscillator strength, f, of the es-absorpsolutions (15) but less than G,,, = 3.2 ob-tion band in hydrazine can be estimated from tained in liquid ammonia (14,19,36,37). the approximation (43).…”

Section: Methodssupporting

confidence: 69%

“…104 and 1.25 x lo4 M-' at 410 and 640 nm, Consequently we find no evidence for a sigrespectively (35). On this basis we find that nificant difference in the extinction coefficients (14,19,36,37,42), this supports the solutions saturated with sodium hydroxide, assumption that E,-(400 nm band) is 4 x lo4 enhances the yield to GeS = 2.65 0.15. This M-' cm-'.…”

Section: Methodssupporting

confidence: 48%

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Pulse radiolytic formation of solvated electrons in hydrazine

Seddon¹,

Fletcher²,

Sopchyshyn³

1976

Can. J. Chem.

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The spectrum and yield of solvated electrons in anhydrous hydrazine have been investigated by pulse radiolysis. At room temperature the optical absorption band has a maximum at 1.22 eV (1015 nm) with a molar extinction coefficient of 2.2 ± 0.1 × 104 M−1 cm−1 and a temperature coefficient of 1.5 × 10−3 eV deg−1 from 7–45 °C. The oscillator strength is estimated to be 0.6. The optical transition energy is in reasonable agreement with an empirical correlation of solvent properties proposed by Freeman provided that only the polarisability of the nitrogen lone-pair electrons contribute to Emax. Comparisons are made with liquid amides which also have lone-pair polarisable groups and with water and liquid ammonia which have physical properties very similar to hydrazine. Electron yields increase from [Formula: see text] in pure hydrazine to 2.65 + 0.15 in basic solutions containing ≥0.1 M sodium hydrazide.

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Section: Methodssupporting

confidence: 69%

Section: Methodssupporting

confidence: 48%

Pulse radiolytic formation of solvated electrons in hydrazine

Seddon¹,

Fletcher²,

Sopchyshyn³

1976

Can. J. Chem.

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“…12 The insensitivity of the yields with changing temperature in the 198-296 K interval, as observed by these authors, is in reasonable agreement with the theoretical prediction.…”

Section: Resultssupporting

confidence: 85%

Solvated electron yields in liquid and supercritical ammonia—A statistical mechanical treatment

Schiller

Horváth

2012

The Journal of Chemical Physics

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Earlier the geminate recombination of ions and solvated electrons, produced by ionizing radiation or laser light, was theoretically treated by a model which consisted of a Rydberg atom interacting with the thermodynamic fluctuations of the medium [R. Schiller, J. Chem. Phys. 92, 5527 (1990)]. The theory was applied to liquid-to-supercritical water [R. Schiller and Á. Horváth, J. Chem. Phys. 135, 084510 (2011)]. Now it is compared with recent experiments performed on liquid-to-supercritical ammonia [J. Urbanek, A. Dahmen, J. Torres-Alacan, P. Königshoven, J. Lindner, and P. Vöhringer, J. Phys. Chem. B 116, 2223 (2012)]. The agreement between theory and experiment seems to be reasonable. The treatment is critically assessed.

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“…Using We also use the experimental data on ω 0 (T ) [58]. This last parameter leads to an implicit temperature dependence of α(ω), we take ∂ω 0 (T )/∂T = −2.…”

Section: E Dielectric and Thermodynamical Propertiesmentioning

confidence: 99%

Nature of the metal-nonmetal transition in metal-ammonia solutions. I. Solvated electrons at low metal concentrations

Chuev,

Quemerais,

Crain

2007

Preprint

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Using a theory of polarizable fluids, we extend a variational treatment of an excess electron to the many-electron case corresponding to finite metal concentrations in metal-ammonia solutions (MAS). We evaluate dielectric, optical, and thermodynamical properties of MAS at low metal concentrations. Our semi-analytical calculations based on a mean-spherical approximation correlate well with the experimental data on the concentration and temperature dependencies of the dielectric constant and the optical absorption spectrum. The properties are found to be mainly determined by the induced dipolar interactions between localized solvated electrons, which result in the two main effects: the dispersion attractions between the electrons and a sharp increase in the static dielectric constant of the solution. The first effect creates a classical phase separation for the light alkali metal solutes (Li, Na, K) below a critical temperature. The second effect leads to a dielectric instability, i.e., polarization catastrophe, which is the onset of metallization. The locus of the calculated critical concentrations is in a good agreement with the experimental phase diagram of Na-NH 3 solutions. The proposed mechanism of the metal-nonmetal transition is quite general and may occur in systems involving self-trapped quantum quasiparticles.

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Absorption spectrum, yield, and decay kinetics of the solvated electron in pulse radiolysis of liquid ammonia at various temperatures

Cited by 24 publications

References 3 publications

Pulse radiolytic formation of solvated electrons in hydrazine

Pulse radiolytic formation of solvated electrons in hydrazine

Solvated electron yields in liquid and supercritical ammonia—A statistical mechanical treatment

Nature of the metal-nonmetal transition in metal-ammonia solutions. I. Solvated electrons at low metal concentrations

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