ABINITIO POTENTIAL CURVES AND COUPLING-MATRIX ELEMENTS FOR CHARGE-TRANSFER FROM H TO N-2+ AND N-3+

Ab initio configuration-interaction methods are used to obtain the potential curves and coupling-matrix elements describing the charge transfer reactions N2+(Po2)+H→N++H+ and N3+(S1)+H→N2++H+. The basis sets are chosen to reproduce efficiently the crossing region and the polarization effects important for coupling-matrix elements. Correlation-energy problems are discussed in the context of rearrangement collisions and procedures are developed to minimize them. The computed reaction energies for the important channels of the reaction are within 7 and 1%, respectively, of the experimental values. © 1979 The American Physical Society.