Structural transitions of ionic microgel solutions driven by circularly polarized electric fields

Abstract

In this work, a theoretical approach is developed to investigate the structural properties of ionic microgels induced by a Circularly Polarized (CP) electric field. Following a similar study on chain formation in the presence of linearly polarized fields [T.\ Colla \textit{et al.}, {\textit ACS Nano}, 2018, \textbf{12}, 4321-4337], we propose an effective potential between microgels which incorporates the field-induced interactions \textit{via} a static, time averaged polarizing charge at the particle surface. In such a coarse-graining framework, the induced dipole interactions are controlled by external parameters such as the field strength and frequency, ionic strength, as well as microgel charge and concentration, thus providing a convenient route to induce different self-assembly scenarios through experimentally adjustable quantities. In contrast to the case of linearly polarized fields, dipole interactions in the case of CP light are purely repulsive in the direction perpendicular to the polarization plane, while featuring an in-plane attractive well. As a result, the CP field induces layering of planar sheets arranged perpendicularly to the field direction, in strong contract to the chain formation observed in the case of linear polarizations. Depending on the field strength and particle concentration, in-plane crystallization can also take place. Combining Molecular Dynamics (MD) simulations and the liquid-state hyppernetted-chain (HNC) formalism, we herein investigate the emergence of layering formation and in-plane crystal ordering as the dipole strength and microgel concentration are changed over a wide region of parameter space.