Exact Solution for the Influence of Spectral Diffusion on Single-Molecule Photon-Statistics

TL;DR

This paper derives an exact analytical formula for the photon emission statistics of a single molecule affected by spectral diffusion, revealing conditions for quantum and classical emission behaviors and how to optimize quantum sub-Poissonian emission.

Contribution

It provides the first exact solution for Mandel's Q parameter considering spectral diffusion effects in single-molecule photon statistics.

Findings

Identifies conditions for transitions between quantum and classical emission regimes.

Shows how to optimize Rabi frequency for strongest quantum sub-Poissonian emission.

Derives an exact analytical formula for photon statistics under spectral diffusion.

Abstract

We investigate the distribution of number of photons emitted by a single molecule undergoing a spectral diffusion process and interacting with a continuous wave field. Using a generating function formalism an exact analytical formula for Mandel's $Q$ parameter is obtained. The solution exhibits transitions between: (i) Quantum sub-Poissonian and Classical super-Poissonian behaviors, and (ii) fast to slow modulation limits. Our solution yields the conditions on the magnitude of the spectral diffusion time scales on which these transitions are observed. We show how to choose the Rabi frequency in such a way that the Quantum sub-Poissonian nature of the emission process becomes strongest, we find ${\Omega^2 \over \Gamma} = {\Gamma_{{\rm SD}} + \Gamma \over 2}$ where $\Gamma_{{\rm SD}}$ ($\Gamma$) is the spectral diffusion (radiative) contribution to the width of the line shape.