Tuning Bimolecular Chemical Reactions by Electric Fields.

We develop a theoretical method for solving the quantum mechanical reactive scattering problem in the presence of external fields based on a hyperspherical coordinate description of the reaction complex combined with the total angular momentum representation for collisions in external fields. The method allows us to obtain converged results for the chemical reaction LiF+H→Li+HF in an electric field. Our calculations demonstrate that, by inducing couplings between states of different total angular momenta, electric fields with magnitudes <150  kV/cm give rise to resonant scattering and a significant modification of the total reaction probabilities, product state distributions, and the branching ratios for reactive versus inelastic scattering.