Concerted Double Hydrogen-Bond Breaking by Intermolecular Coulombic Decay in the Formic Acid Dimer.

Hydrogen bonds are ubiquitous in nature and of fundamental importance to the chemical and physical properties of molecular systems in the condensed phase. Nevertheless, our understanding of the structural and dynamical properties of hydrogen-bonded complexes in particular in electronic excited states remains very incomplete. Here, by using formic acid (FA) dimer as a prototype of DNA base pair, we investigate the ultrafast decay process initiated by removal of an electron from the inner-valence shell of the molecule upon electron-beam irradiation. Through fragment-ion and electron coincident momentum measurements and ab initio calculations, we find that de-excitation of an outer-valence electron at the same site can initiate ultrafast energy transfer to the neighboring molecule, which is in turn ionized through the emission of low-energy electrons. Our study reveals a concerted breaking of double hydrogen-bond in the dimer initiated by the ultrafast molecular rotations of two FA + cations following this nonlocal decay mechanism.