Cage effect in supercooled molecular liquids: local anisotropies and collective solid-like response

Abstract: Both local geometry and collective, extended excitations drive the moves of a particle in the cage of its neighbours in dense liquids. The strength of their influence is investigated by Molecular Dynamics simulations of a supercooled liquid of fully-flexible trimers with semirigid or rigid bonds. The rattling in the cage is investigated on different length scales. First, the rattling anisotropy due to local order is characterized by two order parameters sensing the monomers succeeding or failing to escape from the cage. Then, the collective response of the surroundings excited by the monomer-monomer collisions is considered. The collective response is initially restricted to the nearest neighbours of the colliding particle by a Voronoi analysis revealing elastic contributions. Then, the long-range excitation of the farthest neighbours is scrutinised by searching spatially-extended correlations between the simultaneous fast displacements of the caged particle and the surroundings. It is found that the longitudinal component has stronger spatial modulation than the transverse one with wavelength of about one particle diameter, in close resemblance with experimental findings on colloids. It is concluded that the cage rattling is largely affected by solid-like extended modes.