A density functional theory for patchy colloids based on Wertheim's association theory: beyond the single bonding...

Area of Science:

• Colloid and Surface Science
• Statistical Mechanics
• Computational Chemistry

Background:

• Classical density functional theory (DFT) is a powerful tool for studying fluids.
• Patchy colloids, with specific binding sites, exhibit complex self-assembly behaviors.
• Existing DFT models often struggle with multi-bonding interactions.

Purpose of the Study:

• To develop the first classical density functional theory for patchy colloids capable of multiple bonds per patch.
• To validate the developed theory against simulation data for a model system.
• To assess the theory's ability to predict macroscopic properties like bulk pressure.

Main Methods:

• Development of a novel classical density functional theory based on Wertheim's framework.
• Implementation of Monte Carlo simulations for a system of patchy colloids in a planar slit pore.
• Comparison of theoretical predictions with simulation results for density profiles and bonding fractions.

Main Results:

• The developed DFT shows excellent agreement with Monte Carlo simulations for density profiles.
• The theory accurately predicts bonding fractions, accounting for multi-bonding interactions.
• The theory successfully reproduces bulk pressures from wall contact densities, validating the wall contact rule.

Conclusions:

• The new classical DFT provides a robust theoretical framework for multi-bonding patchy colloids.
• The theory offers a computationally efficient method for predicting the behavior of complex colloidal systems.
• This work advances the understanding of self-assembly in systems with specific, multi-valent interactions.