The X 2 Σ + 1 / 2 , A 2 Π 1 / 2 , A 2 Π 3 / 2 , and B 2 Σ + 1 / 2 potential-energy curves for Rb+He are computed at the spin-orbit multireference configuration interaction level of theory using a hierarchy of Gaussian basis sets at the double-zeta (DZ), triple-zeta (TZ), and quadruple-zeta (QZ) levels of valence quality. Counterpoise and Davidson-Silver corrections are employed to remove basis-set superposition error and ameliorate size-consistency error. An extrapolation is performed to obtain a final set of potential-energy curves in the complete basis-set (CBS) limit. This yields four sets of systematically improved X 2 Σ + 1 / 2 , A 2 Π 1 / 2 , A 2 Π 3 / 2 , and B 2 Σ + 1 / 2 potential-energy curves that are used to compute the A 2 Π 3 / 2 bound vibrational energies, the position of the D 2 blue satellite peak, and the D 1 and D 2 pressure broadening and shifting coefficients, at the DZ, TZ, QZ, and CBS levels. Results are compared with previous calculations and experimental observation.
Physical Review A
Blank, L. A., Sharma, A. R., & Weeks, D. E. (2018). Influence of basis-set size on the X Σ1/2+ 2, A Π1/2 2, A Π3/2 2, and B Σ1/2+ 2 potential-energy curves, A Π3/2 2 vibrational energies, and D1 and D2 line shapes of Rb+He. Physical Review A, 97(3), 032705 (8 pp.). https://doi.org/10.1103/PhysRevA.97.032705