Ab initiopotential curves and coupling-matrix elements for charge transfer from H toN2+andN3+

Ab initio configuration-interaction methods are used to obtain the potential curves and coupling-matrix elements describing the charge transfer reactions ${\mathrm{N}}^{2+}\left({}_{}{}^2{}_{}{}^{}P_{}^o{}_{}{}^{}\right)+\mathrm{H}\to {\mathrm{N}}^{+}+{\mathrm{H}}^{+}$ and ${\mathrm{N}}^{3+}\left({}_{}{}^1{}_{}{}^{}S\right)+\mathrm{H}\to {\mathrm{N}}^{2+}+{\mathrm{H}}^{+}$. 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.