The time scales and formation mechanisms of tri-hydrogen cation products in organic molecule ionization processes are poorly understood, despite their cardinal role in the chemistry of the interstellar medium and in other chemical systems. Using an ultrafast extreme-ultraviolet pump and time-resolved near-IR probe, combined with high-level ab initio molecular dynamics calculations, here we report unambiguously that H3 + formation in double-ionization of methanol occurs on a sub 100 fs time scale, settling previous conflicting findings of strong-field Coulomb explosion experiments. Our combined experimental–computational studies suggest that ultrafast competition, between proton-transfer and long-range electron-transfer processes, determines whether the roaming neutral H2 dynamics on the dication result in H3+ or H2+ fragments respectively.
Bibliographical noteFunding Information:
E.L. and R.B. gratefully thank Drs. Toru Shiozaki (Northwestern University) and Igor Schapiro (Hebrew University) for their advice and help in setting up and using the BAGEL code. We acknowledge funding from the ERC grant #306783 and ISF grants #1369/17 189/14 as well as funding from the Wolfson foundation.
© 2020, The Author(s).