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Tunnelling in collinear light--heavy--heavy reactions

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00496a004· OSTI ID:6378042
For reactions of Mu, H, D, T with F/sub 2/ or Cl/sub 2/, mathematically one-dimensional unsymmetric Eckart barrier permeabilities calculated within the vibrationally adiabatic model agree extremely well with exact quantum collinear reaction probabilities using extended LEPS surfaces. The corresponding rate constants and activation energies, in the temperature interval 230 to 900 K, are also in very good agreement. Other approximations, e.g., the parabolic barrier, have also been tested but are found to be less suitable. In particular, assumption of conservation of vibrational energy leads to considerable errors. 9 figures, 5 tables.
Research Organization:
Vienna Univ., Austria
OSTI ID:
6378042
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:2; ISSN JACSA
Country of Publication:
United States
Language:
English

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