371 research outputs found
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
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