Open quantum system approach to single-molecule spectroscopy

TL;DR

This paper presents an open quantum system framework for single-molecule spectroscopy, enabling a unified quantum-classical description of fluorescence dynamics and optical observables in complex nano-environments.

Contribution

It introduces a microscopic quantum approach that models environmental effects and fluorescence observables within a Lindblad rate equation framework, advancing beyond stochastic models.

Findings

Unified quantum-classical description of fluorescence

Accurate modeling of spectral diffusion and lifetime fluctuations

Calculation of optical spectra and photon statistics

Abstract

In this paper, single-molecule spectroscopy experiments based on continuous laser excitation are characterized through an open quantum system approach. The evolution of the fluorophore system follows from an effective Hamiltonian microscopic dynamic where its characteristic parameters, i.e., its electric dipole, transition frequency, and Rabi frequency, as well as the quantization of the background electromagnetic field and their mutual interaction, are defined in an extended Hilbert space associated to the different configurational states of the local nano-environment. After tracing out the electromagnetic field and the configurational states, the fluorophore density matrix is written in terms of a Lindblad rate equation. Observables associated to the scattered laser field, like optical spectrum, intensity-intensity correlation, and photon-counting statistics, are obtained from a quantum-electrodynamic calculation also based on the effective microscopic dynamic. In contrast with stochastic models, this approach allows to describe in a unified way both the full quantum nature of the scattered laser field as well as the classical nature of the environment fluctuations. By analyzing different processes such as spectral diffusion, lifetime fluctuations, and light assisted processes, we exemplify the power of the present approach.