Elucidating the Nature of π-hydrogen Bonding in Liquid Water and Ammonia

Aromatic compounds form an unusual kind of hydrogen bond with water and ammonia molecules, known as the π-hydrogen bond. In this work, we report ab initio path integral molecular dynamics simulations enhanced by machine-learning potentials to study the structural, dynamical, and spectroscopic properties of solutions of benzene in liquid water and ammonia. Specifically, we model the spatial distribution functions of the solvents around the benzene molecule, establish the π-hydrogen bonding interaction as a prominent structural motive, and set up existence criteria to distinguish the π-hydrogen bonded configurations. These serve as a structural basis to calculate binding affinities of the solvent molecules in πhydrogen bonds, identify an anticooperativity effect across the aromatic ring in water (but not ammonia), and estimate π-hydrogen bond lifetimes in both solvents. Finally, we model hydration-shell-resolved vibrational spectra to clearly identify the vibrational signature of this structural motif in our simulations. These decomposed spectra corroborate previous experimental findings for benzene in water, offer additional insights, and further emphasize the contrast between π-hydrogen bonds in water and in ammonia. Our simulations provide a comprehensive picture of the studied phenomenon and, at the same time, serve as a meaningful ab initio reference for an accurate description of π-hydrogen bonding using empirical force fields in more complex situations, such as the hydration of biological interfaces.