RESUMO
Ultrafast H2+ and H3+ formation from ethanol is studied using pump-probe spectroscopy with an extreme ultraviolet (XUV) free-electron laser. The first pulse creates a dication, triggering H2 roaming that leads to H2+ and H3+ formation, which is disruptively probed by a second pulse. At photon energies of 28 and 32 eV, the ratio of H2+ to H3+ increases with time delay, while it is flat at a photon energy of 70 eV. The delay-dependent effect is ascribed to a competition between electron and proton transfer. High-level quantum chemistry calculations show a flat potential energy surface for H2 formation, indicating that the intermediate state may have a long lifetime. The ab initio molecular dynamics simulation confirms that, in addition to the direct emission, a small portion of H2 undergoes a roaming mechanism that leads to two competing pathways: electron transfer from H2 to C2H4O2+ and proton transfer from C2H4O2+ to H2.