Microcanonical Kinetics of Water-Mediated Proton Transfer in 4ABAH + ·(H 2 O) n = 4–6 Clusters (ABA = Aminobenzoic Acid): A Model System for Size-Dependent Relaxation to Ergodic Behavior

We leverage the unique properties of the 4ABAH + ·(H 2 O) n clusters (ABA = 4-aminobenzoic acid, n = 4–6) to quantitatively address how a finite, isolated system evolves into an ergodic condition starting from localized arrangements in configuration space. This system adopts two distinct structural isomers in which water molecules cluster around the widely separated cationic centers of its two protomers. These isomers arise from excess proton attachment to either the acid ( O ) or amino ( N ) group on opposite sides of the benzene ring. Both forms are captured and kinetically trapped using cryogenic ion methods and then selectively vibrationally excited through their mutually exclusive IR bands involving NH and OH stretching fundamentals. Because the IR excitations lie below the water binding energy, the system can evolve to explore slow, rare events that lead to the interconversion between the two isomers. The rates of these intracluster reactions are determined by using a pump–probe scheme involving ∼5 ns IR pump and UV probe lasers. The rates occur on the microsecond time scale leading to steady state populations of the isomers, thus revealing the cluster size-dependent fractionation between the two species at microcanonical equilibrium. The steady state distributions are correlated with the expected trend in the cluster size-dependent reaction energetics, which are in turn consistent with changes in the relative densities of states of the two species. These results thus provide an unusually clear example in which complex, protic-solvent-mediated chemical transformations are captured within a finite system at a precisely determined internal energy.