19791201
Theoretical study of hotatom chemistry. the T + HD exchange reactions
Publication
Publication
Journal of Physical Chemistry , Volume 83  Issue 8 p. 1033 1042
The hotatom exchange reactions T + HD → TH + D and T + HD → TD + H have been studied by trajectory calculations on the PorterKarplus potential surface up to a laboratory collision energy of 60 eV. The integral reaction probability (IRP) equations for product yields are extended to include the effects of inelastic collisions. The IRP formulas are then reduced to their Monte Carlo form for use with the trajectory calculations. A realistic moderating function P(E,E′) is obtained and resolved into elastic and inelastic contributions. Reactive, nonreactive, and dissociative cross sections are given as a function of energy up to 60 eV. The reaction probabilities are given and reaction mechanisms are discussed. The IRP equations are solved numerically using the realistic and hardsphere moderating functions to obtain absolute TH and TD product yields and the TH/TD product ratio, and compared to the kinetic theory and experimental results. All three theoretical models agree with the experimental result of 0.70 at 2.8 eV. The realistic IRP model gives an inverted isotope ratio of 1.78 at high energy, whereas the simpler models predict an isotope ratio of 0.80, in much closer agreement with experiment. The differences are related to the detailed shape of P(E,E′) and it is shown that the hardsphere and kinetic theory models predict the right result by a combination errors. The need for consideration of secondary collisions in a rigorous treatment is emphasized.
Additional Metadata  

Journal of Physical Chemistry  
Organisation  Department of Chemistry 
Wright, J.S, Gray, S.K. (Stephen K.), & Porter, R.N. (Richard N.). (1979). Theoretical study of hotatom chemistry. the T + HD exchange reactions. Journal of Physical Chemistry, 83(8), 1033–1042.
