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.

Submitted to JCP

References in corpus (2)

• Resummed thermodynamic perturbation theory for bond cooperativity in associating fluids with small bond angles: Effects of steric hindrance and ring formation
• On the cooperativity of association and reference energy scales in thermodynamic perturbation theory

Cited by in corpus (4)

• A molecular equation of state for alcohols which includes steric hindrance in hydrogen bonding
• A general mixture equation of state for double bonding carboxylic acids with >= 2 association sites
• A simple second order thermodynamic perturbation theory for associating fluids
• Nucleation Rates of Water Using Adjusted SAFT-0 EOS