Permutationally symmetric molecular aggregates

Abstract

Linear optical spectra of molecular aggregates are often approximated by classical optics methods such as the discrete-dipole approximation (DDA), coherent exciton scattering (CES), and coherent potential approximation (CPA), where the only quantum-mechanical input to the calculation is the linear susceptibility of the monomers. However, the limits of validity of these classical optics methods remain opaque. Here, starting from a quantum mechanical Hamiltonian for the aggregate, we identify a limit where DDA/CPA/CES is exact: all-to-all coupled permutationally symmetric aggregates of $N \to \infty$ monomers. The permutational symmetry of this molecular version of the Lipkin-Meshkov-Glick model, which is closely related to that of the molecular polariton problem of many identical molecules coupled to a single-cavity mode, allows us to borrow recent techniques developed for the latter. In particular, we identify a $1/N$ expansion that corrects the classical optics limit with finite $N$ corrections to the linear response of the aggregate. These corrections feature as Raman-like transitions of a single monomer. We illustrate these findings with calculations on the very physically-relevant setup of a homodimer. Our findings clarify how quantum optical features that go beyond classical optics can already be present in simple arrays of quantum emitters such as molecular aggregates.