Dynamics of formation of products D2CN+, DCN+, and CD3+ in the reaction of N+ with CD4: a crossed-beam and theoretical study.
The formation of D(2)CN(+) in the reaction of N(+) ((3)P) with CD(4) was studied using the crossed beam technique at collision energies of 3.66 and 4.86 eV. The experiments were complemented by calculations of stationary points on the triplet hypersurface of the system. The scattering data showed that the reaction proceeds by the formation of two intermediate complexes having different lifetimes: a long-lived statistical intermediate and a short-lived complex (mean lifetime about one period of an average rotation) with more energy in translation than the statistical complex. Comparison with theoretical calculations suggests that the long-lived complex leads the CDND(+) isomer of the product ion, whereas the short-lived complex leads prevailingly to the CD(2)N(+) isomer. The product DCN(+) results from further decomposition of the primary product D(2)CN(+), whereas CD(3)(+) is formed both by a hydride-ion transfer and a long-lived complex decomposition.
Zabka
Jan
J
V. Cermák Laboratory, J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, 18223 Prague 8, Czech Republic.
Roithová
Jana
J
Spanel
Patrik
P
Herman
Zdenek
Z