English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Plus monthly

Global: Zendy Tools annual

Global: Zendy Tools monthly

Global: Zendy Free Plan

A system of patchy colloidal particles interacting with a solute that canassociate multiple times in any direction is a useful model for patchycolloidal mixtures. Despite the simplicity of the interaction, because of thepresence of multi-body correlations predicting the thermodynamics of suchsystems remains a challenge. Earlier Marshall and Chapman developed amulti-body formulation for such systems wherein the cluster partition functionfor the hard-sphere solvent molecules in a defined inner-shell (or coordinationvolume) of the hard-sphere solute is used as the reference within thestatistical association fluid theory formalism. The multi-body contribution tothese partition functions are obtained by ignoring the bulk solvent, thuslimiting the applicability of the theory to low system densities. Derivinginspiration from the quasichemical theory of solutions where these partitionfunctions occur in the guise of equilibrium constants for cluster formation, wedevelop a way to account for the multi-body correlations including the effectof the bulk solvent. We obtain the free energy to evacuate the inner-shell, thechemistry contribution within quasichemical theory, from simulations of thehard-sphere reference. This chemistry contribution reflects association in thereference in the presence of the bulk medium. The gas-phase partition functionsare then augmented by a mean activity factor that is adjusted to reproduce thechemistry contribution. We show that the updated partition function provides arevised reference that better captures the distribution of solvent around thesolute up to high system densities. Using this updated reference, we find thattheory better describes both the bonding state and the excess chemicalpotential of the colloid in the physical system.

Incorporating multi-body effects in SAFT by improving the description of  the reference system. I. Mean activity correction for cluster integrals in  the reference system