Ultrafast Roaming Mechanisms in Ethanol Probed by Intense Extreme Ultraviolet Free-Electron Laser Radiation: Electron Transfer versus Proton Transfer

Abstract

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 <i>ab initio</i> 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.