The Quantum Normal Form Approach to Reactive Scattering: The Cumulative Reaction Probability for Collinear Exchange Reactions

The quantum normal form approach to quantum transition state theory is used to compute the cumulative reaction probability for collinear exchange reactions. It is shown that for heavy atom systems like the nitrogen exchange reaction the quantum normal form approach gives excellent results and has major computational benefits over full reactive scattering approaches. For light atom systems like the hydrogen exchange reaction however the quantum normal approach is shown to give only poor results. This failure is attributed to the importance of tunnelling trajectories in light atom reactions that are not captured by the quantum normal form as indicated by the only very slow convergence of the quantum normal form for such systems.
Published in the Journal of Chemical Physics, v131 p144103-1 - 144103-8, 2009.