Thermodynamics of water modeled using ab initio simulations

We regularize the potential distribution framework to calculate the excess free energy of liquid water simulated with the BLYP-D density functional. The calculated free energy is in fair agreement with experiments but the excess internal energy and hence also the excess entropy are not. Our work emphasizes the importance of thermodynamic characterization in assessing the quality of electron density functionals in describing liquid water and hydration phenomena

Quasichemical theory and the description of associating fluids relative to a reference: Multiple bonding of a single site solute

We derive an expression for the chemical potential of an associating solute in a solvent relative to the value in a reference fluid using the quasichemical organization of the potential distribution theorem. The fraction of times the solute is not associated with the solvent, the monomer fraction, is expressed in terms of (a) the statistics of occupancy of the solvent around the solute in the reference fluid and (b) the Widom factors that arise because of turning on solute-solvent association. Assuming pair-additivity, we expand the Widom factor into a product of Mayer f-functions and the resulting expression is rearranged to reveal a form of the monomer fraction that is analogous to that used within the statistical associating fluid theory (SAFT). The present formulation avoids all graph-theoretic arguments and provides a fresh, more intuitive, perspective on Wertheim's theory and SAFT. Importantly, multi-body effects are transparently incorporated into the very foundations of the theory. We illustrate the generality of the present approach by considering examples of multiple solvent association to a colloid solute with bonding domains that range from a small patch on the sphere, a Janus particle, and a solute whose entire surface is available for association

Hydration and mobility of HO-(aq)

The hydroxide anion plays an essential role in many chemical and biochemical reactions. But a molecular-scale description of its hydration state, and hence also its transport, in water is currently controversial. The statistical mechanical quasi-chemical theory of solutions suggests that HO[H2O]3- is the predominant species in the aqueous phase under standard conditions. This result is in close agreement with recent spectroscopic studies on hydroxide water clusters, and with the available thermodynamic hydration free energies. In contrast, a recent ab initio molecular dynamics simulation has suggested that HO[H_2O]4- is the only dominant aqueous solution species. We apply adiabatic ab initio molecular dynamics simulations, and find good agreement with both the quasi-chemical theoretical predictions and experimental results. The present results suggest a picture that is simpler, more traditional, but with additional subtlety. These coordination structures are labile but the tri-coordinate species is the prominent case. This conclusion is unaltered with changes in the electronic density functional. No evidence is found for rate-determining activated inter-conversion of a HO[H2O]4- trap structure to HO[H2O]3-, mediating hydroxide transport. The view of HO- diffusion as the hopping of a proton hole has substantial validity, the rate depending largely on the dynamic disorder of the water hydrogen-bond network.Comment: 7 pages, 5 figures, additional results include