The effect of shape, polydispersity, charge, and fraction of crystallite bundles on the cholesteric pitch of cellulose nanocrystal suspensions.

Using Onsager-Straley's second-virial theory, we investigate the cholesteric pitch of cellulose nanocrystal (CNC) suspensions. We model the CNCs as hard chiral bundles of microfibrils and examine the effect of the shape of these chiral bundles, characterized by aspect ratio and chirality, on the cholesteric pitch. Additionally, we explore the impact of length polydispersity and surface charge on the cholesteric phase of CNCs. Furthermore, we consider binary mixtures of twisted bundles and achiral primary crystallites to provide a more realistic representation of CNC suspensions. Our findings reveal that the degree of bundle twisting significantly affects the helical twisting of the cholesteric phase. We also observe that the average particle length and length polydispersity have substantial effects on strongly twisted bundles but minimal effects on weakly twisted ones. Finally, our study indicates that as the range of electrostatic interactions increases, the transfer of chirality from the microscopic to macroscopic length scales becomes masked, resulting in an increase in the cholesteric pitch. In the case of binary mixtures, the bundles act as chiral dopants, and an increasing fraction of bundles progressively enhances the helical twisting of the cholesteric phase.

Ground State Configurations and Metastable Phases of Charged Linear Rods.

This computational study investigates the energy minimum, that is, ground state, of suspensions of monodisperse (single-component) charged linear rods at various densities and screening lengths. We find that closed-packed unidirectional configurations have the lowest energies for all studied cases. We further specify the lattice parameters for these crystalline structures. In addition, we identify a few metastable phases, including heliconical structures. These metastable heliconical phases are composed of hexagonal smectic C layers with particle orientations forming a conical helicoid with a short pitch of three layers. We evidence this by zero-temperature Monte Carlo simulations starting from an energy-minimized hexagonal cholesteric configuration, which rapidly transforms to a heliconical phase. Furthermore, this heliconical phase is remarkably stable even at finite temperatures and melts to a disordered phase at high temperatures. Finally, we conduct simulations at room temperature and conditions typical for cellulose nanocrystal suspensions to study the onset of nematic order and compare our results to available experimental data. Our findings suggest that electrostatics play an important role in the isotropic/anisotropic transition for dense suspensions of charged rods.