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The Hþ þ H and Dþ þ D collisions represent the simplest examples of collisions involving identical fermions and bosons, respectively. We report a study of these collisions in the range of energies corresponding to 0–40 K at a resolution of 100 mK based on a half-collision approach. Using the technique of pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy (PFI-ZEKE-PES), which relies on the pulsed field ionization of nonpenetrating Rydberg states of very high principal quantum number (n ≥ 250), we have measured the positions and widths of all low-lying shape resonances of this collision and compare them with the results of ab initio calculations that consider nonadiabatic, relativistic, and radiative corrections to the Born-Oppenheimer energies. Excellent agreement between calculated and measured widths and positions is found except for the Xþðvþ 1⁄4 25; Nþ 1⁄4 8Þ shape resonance, the width of which is calculated to be narrower than observed. Comparison with similar observations made for the Hþ þ H collision [Beyer and Merkt Phys. Rev. Lett. 116, 093001 (2016)] indicates that the shape resonances measured by PFI-ZEKE-PES are broadened by the effects of the localization of the charge of the dissociating ion core arising from a nonadiabatic coupling between ion core and Rydberg electron. A simple model is presented that enables one to predict which shape resonances are likely to be affected and to correct for the resulting broadening. Two shape resonances of D2þ, the Xþðvþ1⁄426;Nþ1⁄45Þ and the Aþðvþ 1⁄4 0; Nþ 1⁄4 5Þ resonances, have electric-dipole-allowed transitions to bound states of D2þ and are shown to facilitate the radiative association at low temperature. The results are used to determine the elastic cross sections of the Hþ þ H and Dþ þ D collisions for partial waves up to Nþ 1⁄4 11 and the radiative-association cross sections and rate constants in the range between 10 mK and 100 000 K.

physical review. x

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