Optical Activity from the Exciton Aharonov–Bohm Effect: A Floquet Engineering Approach

Abstract

Floquet engineering is a convenient strategy to induce nonequilibrium phenomena in molecular and solid-state systems, or to dramatically alter the physicochemical properties of matter, bypassing costly and time-consuming synthetic modifications. In this article, we investigate theoretically some interesting consequences of the fact that an originally achiral molecular system can exhibit nonzero circular dichroism (CD) when it is driven with elliptically polarized light. More specifically, we consider an isotropic ensemble of small cyclic molecular aggregates in solution whose local low-frequency vibrational modes are driven by an elliptically polarized continuous-wave infrared pump. We attribute the origin of a nonzero CD signal to time-reversal symmetry breaking due to an excitonic Aharonov-Bohm (AB) phase arising from a time-varying laser electric field, together with coherent interchromophoric exciton hopping. The obtained Floquet engineered excitonic AB phases are far more tunable than analogous magnetically-induced electronic AB phases in nanoscale rings, highlighting a virtually unexplored potential that Floquet engineered AB phases have in the coherent control of molecular processes and simultaneously introducing new analogues of magneto-optical effects in molecular systems which bypass the use of strong magnetic fields.