Incorporating QM/MM molecular dynamics into the few-mode quantization approach for light-matter interactions in nanophotonic structures

TL;DR

This paper develops a new computational framework combining QM/MM molecular dynamics with few-mode quantization to accurately simulate light-matter interactions in complex nanophotonic environments, accounting for disorder and inhomogeneity.

Contribution

It introduces a general approach that couples ab initio QM/MM dynamics with few-mode field quantization for nanoscale light-matter interaction simulations.

Findings

Strong coupling persists despite molecular disorder.

Symmetry-protected degeneracies are lifted by inhomogeneity.

Field inhomogeneity influences energy transfer pathways.

Abstract

In the context of light-matter interactions between organic chromophores and confined photons of (plasmonic) nano-resonators, we introduce a general framework that couples ab initio QM/MM molecular dynamics with few-mode field quantization to simulate light-matter interactions of molecular emitters at the nanoscale. Arbitrary, lossy, and spatially inhomogeneous photonic environments are represented by a minimal set of interacting modes fitted to their spectral density, while geometry-dependent molecular properties are computed on the fly. Applications to few-molecule strong coupling show that strong coupling persists when molecular degrees of freedom and disorder are included for the chosen system consisting of a nanoparticle dimer coupled to multiple emitters. At the same time, symmetry-protected degeneracies of two-level models are lifted. The framework further reveals how spatial field inhomogeneity and molecular disorder shape cavity-mediated energy transfer, illustrated for an HBQ-Methylene Blue donor-acceptor combination in a five-emitter system.