A structure–dynamics relationship enables prediction of the water hydrogen bond exchange activation energy from experimental data

Abstract

It has long been understood that the structural features of water are determined by hydrogen bonding (H-bonding) and that the exchange of, or “jumps” between, H-bond partners underlies many of the dynamical processes in water. Despite the importance of H-bond exchanges there is, as yet, no direct method for experimentally measuring the timescale of the process or its associated activation energy. Here, we identify and exploit relationships between water's structural and dynamical properties that provide an indirect route for determining the H-bond exchange activation energy from experimental data. Specifically, we show that the enthalpy and entropy determining the radial distribution function in liquid water are linearly correlated with the activation energies for H-bond jumps, OH reorientation, and diffusion. Using temperature-dependent measurements of the radial distribution function from the literature, we demonstrate how these correlations allow us to infer the value of the jump activation energy, E_a,0, from experimental results. This analysis gives E_a,0 = 3.43 kcal mol⁻¹, which is in good agreement with that predicted by the TIP4P/2005 water model. We also illustrate other approaches for estimating this activation energy consistent with these estimates.