Hyperfine-interaction-induced g/u mixing and its implication on the existence of the first excited vibrational level of the A +   Σ u + 2 state of H 2 + and on the scattering length of the H + H+ collision.

Ab initio calculations of the energy level structure of H 2 + that include relativistic and radiative corrections to nonrelativistic energies and the diagonal part of the hyperfine interaction have predicted the existence of four bound rovibrational levels [(v = 0, N = 0 - 2) and (v = 1, N = 0)] of the first electronically excited ( A +   Σ u + 2 ) state of H 2 + , the (v = 1, N = 0) level having a calculated binding energy of only E b = 1.082 219 8(4)·10-9 Eh and leading to an extremely large scattering length of 750(5) a0 for the H+ + H collision [J. Carbonell et al., J. Phys. B: At., Mol. Opt. Phys. 37, 2997 (2004)]. We present an investigation of the nonadiabatic coupling between the first two electronic states ( X +   Σ g + 2 and A +   Σ u + 2 ) of H 2 + induced by the Fermi-contact term of the hyperfine-coupling Hamiltonian. This interaction term, which mixes states of total spin quantum number G = 1/2, is rigorously implemented in a close-coupling approach to solve the spin-rovibronic Schrödinger equation. We show that it mixes states of gerade and ungerade electronic symmetry, that it shifts the positions of all weakly bound rovibrational states of H 2 + , and that it affects both the positions and widths of its shape resonances. The calculations demonstrate that the G = 1/2 hyperfine component of the A+ (v = 1, N = 0) state does not exist and that, for G = 1/2, the s-wave scattering lengths of the H+ + H(1s) collision are -578(6) a0 and -43(4) a0 for the F = 0 and F = 1 hyperfine components of the H(1s) atom, respectively. The binding energy of the G = 3/2 hyperfine component of the A+ (v = 1, N = 0) state is not significantly affected by the hyperfine interaction and the corresponding scattering length for the H+ + H(1s, F = 1) collision is 757(7) a0.