Formally exact fluorescence spectroscopy simulations for mesoscale molecular aggregates with N⁰ scaling

2025/03/01 by Tarun Gera, Gera, Tarun, Alexia Hartzell +7 · 1 citation
Materials Science · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Material Dynamics and Properties #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.48550/arxiv.2503.00584

openalex publication_date 2025/03/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

We present a size-invariant (i.e., N⁰) scaling algorithm for simulating fluorescence spectroscopy in large molecular aggregates. We combine the dyadic adaptive hierarchy of pure states (DadHOPS) equation-of-motion with an operator decomposition scheme and an efficient Monte Carlo sampling algorithm to enable a formally exact, local description of the fluorescence spectrum in large molecular aggregates. Furthermore, we demonstrate that the ensemble average inverse participation ratio (IPR) of DadHOPS wave functions reproduces the delocalization extent extracted from fluorescence spectroscopy of J-aggregates with strong vibronic transitions. This work provides a computationally efficient framework for fluorescence simulations, offering a new tool for understanding the optical properties of mesoscale molecular systems.

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