Radiation products and tunneling process in ionic glasses. 1. Radiation products and recombination in undoped nitrate and acetate glasses

Aaron Barkatt, Charles Angell, John R. Miller

Research output: Contribution to journalArticle

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Abstract

Ionizing radiation acts on 3:2 KNO3-Ca(NO3)2 glasses to produce a simple hole center, the NO3 radical, and an excess electron center, which is probably the NO3 2- radical. At 297 K, 10-6 s after a 4-ns pulse of radiation a yield of 3.2 ± 0.2 ion pairs is found per 100 eV of absorbed energy. The ion pairs recombine, as observed by following the red absorption of NO3max 615 nm), from 10-6 to 102 s. Diffusion of the reacting species is involved above the glass transition temperature (Tg = 341 K), while electron tunneling seems to be the main mechanism below Tg. The reaction is weakly temperature dependent (EA ≃ 3 kcal) from 77 to 260 K, but EA jumps to ≈ 18 kcal above 260 K. These results are discussed in terms of modern electron-transfer theories, which predict such a transition from weak to strong activation. Acetate glasses showed no detectable radiation coloration in the visible, and only a small, decaying absorption in the near UV.

Original languageEnglish (US)
Pages (from-to)2143-2148
Number of pages6
JournalJournal of Physical Chemistry
Volume82
Issue number20
StatePublished - 1978
Externally publishedYes

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Nitrates
nitrates
acetates
Acetates
Ions
Radiation
Glass
Electron tunneling
Electrons
glass
Ionizing radiation
radiation
products
Electron transitions
electron tunneling
ionizing radiation
glass transition temperature
electron transfer
ions
Chemical activation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Radiation products and tunneling process in ionic glasses. 1. Radiation products and recombination in undoped nitrate and acetate glasses. / Barkatt, Aaron; Angell, Charles; Miller, John R.

In: Journal of Physical Chemistry, Vol. 82, No. 20, 1978, p. 2143-2148.

Research output: Contribution to journalArticle

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N2 - Ionizing radiation acts on 3:2 KNO3-Ca(NO3)2 glasses to produce a simple hole center, the NO3 radical, and an excess electron center, which is probably the NO3 2- radical. At 297 K, 10-6 s after a 4-ns pulse of radiation a yield of 3.2 ± 0.2 ion pairs is found per 100 eV of absorbed energy. The ion pairs recombine, as observed by following the red absorption of NO3 (λmax 615 nm), from 10-6 to 102 s. Diffusion of the reacting species is involved above the glass transition temperature (Tg = 341 K), while electron tunneling seems to be the main mechanism below Tg. The reaction is weakly temperature dependent (EA ≃ 3 kcal) from 77 to 260 K, but EA jumps to ≈ 18 kcal above 260 K. These results are discussed in terms of modern electron-transfer theories, which predict such a transition from weak to strong activation. Acetate glasses showed no detectable radiation coloration in the visible, and only a small, decaying absorption in the near UV.

AB - Ionizing radiation acts on 3:2 KNO3-Ca(NO3)2 glasses to produce a simple hole center, the NO3 radical, and an excess electron center, which is probably the NO3 2- radical. At 297 K, 10-6 s after a 4-ns pulse of radiation a yield of 3.2 ± 0.2 ion pairs is found per 100 eV of absorbed energy. The ion pairs recombine, as observed by following the red absorption of NO3 (λmax 615 nm), from 10-6 to 102 s. Diffusion of the reacting species is involved above the glass transition temperature (Tg = 341 K), while electron tunneling seems to be the main mechanism below Tg. The reaction is weakly temperature dependent (EA ≃ 3 kcal) from 77 to 260 K, but EA jumps to ≈ 18 kcal above 260 K. These results are discussed in terms of modern electron-transfer theories, which predict such a transition from weak to strong activation. Acetate glasses showed no detectable radiation coloration in the visible, and only a small, decaying absorption in the near UV.

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