Comparison of radiolysis of cyclopentane, 2,3-dimethylbutane, and neopentane at 4.2 K with that at 77 K as studied by analysis of dimer products

Tilquin, Bernard; Guyot, Beatrice; Miyazaki, Tsuyoshi; Lee, Yi–Chia

doi:10.1016/1359-0197(89)90023-4

Cited by 2 publications

(2 citation statements)

References 23 publications

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“…The present results suggest that the rate of hydrogen atom tunneling from alkane molecules in cryogenic solids is very sensitive to the steric hindrance by the solids to the deformation of the molecules during the tunneling. This may give a reason that the kind of alkyl radicals and the resultant stable products generated by γ-irradiation of organic solids depend on the physical nature of the solids. − …”

Section: Discussionmentioning

confidence: 99%

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Matrix Effect on Hydrogen Atom Tunneling from Alkane to Free Deuterium Atoms in Cryogenic Solid

et al. 1999

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ESR study on alkyl radicals generated in deuterated organic matrixes at 77 K by hydrogen atom tunneling from alkane molecules to free deuterium atoms has been carried out for elucidating control factors for the tunneling. For small alkane molecules, the tunneling rate is determined by the height of the potential energy barrier for the tunneling. For larger molecules in glassy matrixes, the rate decreases with increasing number and length of alkyl chains bonded to a carbon atom to be hydrogen abstracted. The tunneling rate from antepenultimate tertiary carbon is much slower than that from penultimate secondary carbon, even the potential energy barrier is lower. This abnormal effect is explained as being due to the steric hindrance by matrix molecules to the deformation of alkane molecules during the reaction. The alkyl chains surrounded by matrix molecules prevent the deformation of the chemical bonds of the carbon atom from the initial sp3 to the final sp2 configuration, which may cause the increase of the thickness of the potential energy barrier and thereby decrease of the tunneling rate. Free deuterium atoms in a crystalline adamantane matrix selectively abstract hydrogen atoms from the antepenultimate tertiary carbon, probably due to less steric hindrance to the deformation.

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Section: Discussionmentioning

confidence: 99%

“…This may give a reason that the kind of alkyl radicals and the resultant stable products generated by γ-irradiation of organic solids depend on the physical nature of the solids. [19][20][21][22][23][24]…”

Section: Discussionmentioning

confidence: 99%

Matrix Effect on Hydrogen Atom Tunneling from Alkane to Free Deuterium Atoms in Cryogenic Solid

et al. 1999

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The effect of ultralow temperature on olefin cation formation by ionic fragmentation in the radiolysis of 2,3-dimethylbutane

Miyazaki

1991

International Journal of Radiation Applications and Instrumenta

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Comparison of radiolysis of cyclopentane, 2,3-dimethylbutane, and neopentane at 4.2 K with that at 77 K as studied by analysis of dimer products

Cited by 2 publications

References 23 publications

Matrix Effect on Hydrogen Atom Tunneling from Alkane to Free Deuterium Atoms in Cryogenic Solid

Matrix Effect on Hydrogen Atom Tunneling from Alkane to Free Deuterium Atoms in Cryogenic Solid

The effect of ultralow temperature on olefin cation formation by ionic fragmentation in the radiolysis of 2,3-dimethylbutane

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