Pseudorotation and N-body Forces in an Optical Matter System

Abstract

Isomerization in molecular systems almost invariably occurs through 3-dimensional motion due to the nature of chemical bonding. Pseudorotation is an unusual type of isomerization that occurs in some high symmetry systems that gives the appearance of rigid-body rotation yet only involves atom rearrangements. This paper demonstrates that pseudorotation occurs in 2-dimensions in an optical matter (OM) system of metal nanoparticle constituents. The difference in dimensionality of the dynamics arises from the electrodynamic field-interference nature of optical binding vs. quantum mechanical bonding in polyatomic molecules. The 8-nanoparticle OM "kite" structure we study in experiments and simulations has D2 (D2h) symmetry and a D4 symmetric transition state. The mechanism for pseudorotation involves correlated motion of all 8 nanoparticles with smooth (continuous) evolution of their interactions and without particles jumping in or out of the OM array. While the OM kite structure only occurs with 10% probability vs. other OM isomers, its rate of pseudorotation is rapid relative to transitions to other structural isomers (e.g., "teardrop"). The other isomers have structures that lie on a trigonal lattice with inter-particle separations at distances that enhance field interference and induced polarizations. Even though the kite isomer has inter-particle separations that would manifest destructive interference on a particle pair (i.e., 2-body) basis, the kite structure is the slowest to rearrange into any other isomer. We show that the unusual structure and dynamics of the kite optical matter system result from N-body interactions and forces demonstrating that N-body effects are important in this class of active matter and presumably more generally.