CONTRACTED BASIS FUNCTIONS FOR VARIATIONAL SOLUTIONS OF QUANTUM-MECHANICAL REACTIVE SCATTERING PROBLEMS

A new method for constructing efficient basis functions for ℒ2 variational calculations of quantum mechanical rearrangements is presented and tested. With this method, using the same contracted basis functions for all channels in a given vibrational manifold, we can obtain reactive transition probabilities for F + H2 → H + HF(v′). where v′ is the final vibrational state, that are accurate to 0.01 absolute accuracy or 5% relative accuracy with 40% less basis functions than are required for the same accuracy using primitive basis sets and with 60% less basis functions than were used for our previous calculations that were converged to 1%. © 1990 American Chemical Society.