Landscape of kinetically trapped binary assemblies.

Area of Science:

• Physical Chemistry
• Materials Science
• Statistical Mechanics

Background:

• Two-component assemblies exhibit inherent structure diagrams (ISDs) relating inter-subunit energies to kinetic traps (inherent structures).
• ISDs are known to partition into plateaux with uniform stoichiometries and morphologies.
• Structures from specific plateaux are robust outcomes of non-equilibrium growth, suggesting ISD utility in predicting assembly outcomes.

Purpose of the Study:

• To analytically determine how inherent structure diagrams (ISDs) are apportioned into distinct plateaux.
• To elucidate the source of morphologically distinct structures within each ISD plateau.
• To develop a framework for characterizing local properties of trapped structures within ISD plateaux.

Main Methods:

• Development of an analytical treatment for two-component inherent structure diagrams (ISDs).
• Identification of a single, unitless order parameter governing ISD apportionment.
• Characterization of local properties of trapped structures using the analytical framework.

Main Results:

• The apportionment of any two-component ISD into distinct plateaux is shown to arise from a single, unitless order parameter.
• The analytical framework enables the characterization of local properties within each ISD plateau.
• Distinct morphologies observed in different plateaux are linked to the underlying energetic landscape described by the order parameter.

Conclusions:

• A fundamental understanding of ISD apportionment and plateau formation is established through a single order parameter.
• The analytical framework provides insights into the origins of morphological diversity in self-assembling systems.
• This work offers a pathway for the rational design of novel classes of robust non-equilibrium assemblies.