Hydrogen abstraction by methyl radicals in glasses

  1. Get@NRC: Hydrogen abstraction by methyl radicals in glasses (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1039/DC9847800175
AuthorSearch for: ; Search for: ; Search for: ; Search for:
Journal titleFaraday Discussions of the Chemical Society
Pages175191; # of pages: 17
AbstractAn experimental and theoretical study is reported of the abstraction of hydrogen atoms by methyl radicals from organic glasses, in particular methanol and several of its deuterated analogues. Rate constants are obtained for hydrogen and deuterium transfer as a function of temperature for a distribution of trapping sites of the radical in the glass. The site dependence is investigated by an analysis of the non-exponential decay of the methyl radical concentration based on the use of Laplace transforms. With the help of a recently developed theoretical model for hydrogen tunnelling, a relationship between tunnelling rate and tunnelling distance is established on the basis of these observations. The results yield a detailed picture of the structure of the trapping sites: roughly spherical cages in which the tumbling radical is surrounded on average by eleven rotating methyl groups, with the closest of which it reacts. The model yields a quantitative description of the rate of this reaction, expressed in terms of spectroscopic, thermodynamic and quantum-chemical input parameters.
Publication date
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276725
Export citationExport as RIS
Report a correctionReport a correction
Record identifier7175449e-3ea4-425c-afa2-c52855cf91ac
Record created2015-10-13
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)