A second order thermodynamic perturbation theory for hydrogen bond cooperativity in water

Abstract

It has been extensively demonstrated through first principles quantum mechanics calculations that water exhibits strong hydrogen bond cooperativity. Classical molecular simulation and statistical mechanics methods typically assume pairwise additivity, meaning they cannot account for these 3-body and higher cooperative effects. In this document, we extend second order thermodynamic perturbation theory to correct for hydrogen bond cooperativity in 4 site water. We show that the association theory gives substantially different predictions than the first order result, which does not include hydrogen bond cooperativity. By comparison to spectroscopy, neutron diffraction and molecular simulation data, we show that the theory accurately predicts the hydrogen bonding structure of water as a function of temperature and density.