Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

arXiv:cond-mat/0605018 · The Journal of Physical Chemistry B

Single Molecule Photon Counting Statistics for Quantum Mechanical Chromophore Dynamics

Golan Bel, Yujun Zheng, Frank L. H. Brown

Published Sep 21, 2006• 29 citations
arXivHTMLPDF

Abstract

We extend the generating function technique for calculation of single molecule photon emission statistics (Zheng, Y.; Brown, F. L. H. Phys. Rev. Lett. 2003, 90, 238305) to systems governed by multi-level quantum dynamics. This opens up the possibility to study phenomena that are outside the realm of purely stochastic and mixed quantum-stochastic models. In particular, the present methodology allows for calculation of photon statistics that are spectrally resolved and subject to quantum coherence. Several model calculations illustrate the generality of the technique and highlight quantitative and qualitative differences between quantum mechanical models and related stochastic approximations when they arise. Calculations suggest that studying photon statistics as a function of photon frequency has the potential to reveal more about system dynamics than the usual broadband detection schemes.

DOI
10.1021/jp062345v

Related papers

Single molecule photon emission statistics of driven three-level systems

Yonggang Peng, Yujun Zheng, Frank L. H. Brown

We study the statistics of photon emission from three-level single molecule systems. The generating function method [Y. Zheng and F. L. H. Brown, Phys. Rev. Lett. 90, 238305 (2003)] is used to calculate steady state absorption line shapes and Mandel's Q parameter as a function of excitation frequency, as well as the time dependence associated with approach to the steady state. The line shape calculations confirm known results derived via other methods, while the Q parameter results display complex frequency dependences not amenable to simple interpretation. This study confirms the applicability of the generating function formalism to multilevel quantum systems, including the proper modeling of quantum coherence effects.

The Journal of Chemical Physics•Mar 13, 2007•39 citations

Single molecule photon emission statistics in the slow modulation limit

Yujun Zheng, Frank L. H. Brown

A framework for calculating photon emission statistics for single chromophores perturbed by slow environmental fluctuations is introduced. When internal chromophore dynamics are significantly faster than time scales for environmental modulation it becomes possible to invoke a type of adiabatic approximation, allowing for straightforward calculation of photon counting moments including explicitly quantum effects. Unlike previous exact treatments, the present methodology involves calculation of dynamics reflecting only the modulation characteristics of the environment and quantum dynamics of an isolated chromophore separately, i.e., the complicated intermingling of chromophore quantum dynamics and the environmental modulation are suppressed via the adiabatic approximation. This leads to significant conceptual and computational simplifications. Within its regime of applicability, the present approximation reproduces exact calculations quantitatively. We demonstrate this accuracy explicitly for the case of a two-level chromophore modulated by a number of different stochastic models.

The Journal of Chemical Physics•Oct 12, 2004•30 citations

Theory of single molecule emission spectroscopy

Golan Bel, Frank L. H. Brown

A general theory and calculation framework for the prediction of frequency-resolved single molecule photon counting statistics is presented. Expressions for the generating function of photon counts are derived, both for the case of naive "detection" based solely on photon emission from the molecule and also for experimentally realizable detection of emitted photons, and are used to explicitly calculate low-order photon-counting moments. The two cases of naive detection versus physical detection are compared to one another and it is demonstrated that the physical detection scheme resolves certain inconsistencies predicted via the naive detection approach. Applications to two different models for molecular dynamics are considered: a simple two-level system and a two-level absorber subject to spectral diffusion.

The Journal of Chemical Physics•May 4, 2015•1 citation

Single-Molecule Photon Counting Statistics via Generalized Optical Bloch Equations

Yujun Zheng, Frank L. H. Brown

We derive the generating function for single molecule photon emission events within the context of the stochastically modulated optical Bloch equations. Statistical properties of single molecule photon counting experiments are deduced from a set of coupled differential equations only slightly more complicated than the Bloch equations themselves. This formulation allows for the study of photon bunching and antibunching within a single theoretical framework and provides a description of these behaviors that emphasizes the connection with single molecule experiments. Application is made to the spectroscopy of a chromophore coupled to a single two level system.

Physical Review Letters•Jun 13, 2003•129 citations

Theoretical modeling of single-molecule fluorescence with complicated photon statistics

Игорь Сергеевич Осадько, А. В. Наумов, Ivan Yu. Eremchev +2 more

The use of techniques for analyzing the fluorescence photon statistics of a single molecule for modeling single-emitter dynamics is demonstrated. The photon distribution function measured in the fluorescence of a single tetra-tert-butylterrylene molecule embedded in polyisobutylene is used to devise a theoretical model for single emitters with complicated fluorescence photon statistics. Our analysis was carried out with the theoretical approach developed by Osad'ko and co-workers [J. Chem. Phys. 130, 064904 (2009); J. Phys. Chem. C 114, 10349 (2010)] for photon distribution functions. Although the experimental data were obtained at cryogenic temperature where narrow zero-phonon lines are present, the method is based on a purely statistical approach and does not require spectrally resolved data. It can also be applied to the analysis of broad fluorescence bands as measured at room temperature. Therefore, the method has prospects for revealing the quantum dynamics of single biological objects and other single quantum emitters in ambient conditions.

Physical Review A•Nov 5, 2012•14 citations

Single molecule photon emission statistics for non-Markovian blinking models

Yujun Zheng, Frank L. H. Brown

The statistics of photon emission from a single molecule under continuous wave excitation are considered. In particular, we study stochastic model systems where photon emission rates evolve in time with non-Markovian dynamics. Our calculations are based on the recently introduced generalized optical Bloch equation (GBE) formalism, but with numerical complications beyond those seen in previous Markovian stochastic models. A spectral representation is introduced to facilitate the numerical solution of the GBE equations for these more challenging cases.

The Journal of Chemical Physics•Jul 30, 2004•44 citations
We extend the generating function technique for calculation of single molecule photon emission statistics (Zheng, Y.; Brown, F. L. H. Phys. Rev. Lett. 2003, 90, 238305) to systems governed by multi-level quantum dynamics. This opens up the possibility to study phenomena that are outside the realm of purely stochastic and mixed quantum-stochastic models. In particular, the present methodology allows for calculation of photon statistics that are spectrally resolved and subject to quantum coherence. Several model calculations illustrate the generality of the technique and highlight quantitative and qualitative differences between quantum mechanical models and related stochastic approximations when they arise. Calculations suggest that studying photon statistics as a function of photon frequency has the potential to reveal more about system dynamics than the usual broadband detection schemes.
We study the statistics of photon emission from three-level single molecule systems. The generating function method [Y. Zheng and F. L. H. Brown, Phys. Rev. Lett. 90, 238305 (2003)] is used to calculate steady state absorption line shapes and Mandel's Q parameter as a function of excitation frequency, as well as the time dependence associated with approach to the steady state. The line shape calculations confirm known results derived via other methods, while the Q parameter results display complex frequency dependences not amenable to simple interpretation. This study confirms the applicability of the generating function formalism to multilevel quantum systems, including the proper modeling of quantum coherence effects.
A framework for calculating photon emission statistics for single chromophores perturbed by slow environmental fluctuations is introduced. When internal chromophore dynamics are significantly faster than time scales for environmental modulation it becomes possible to invoke a type of adiabatic approximation, allowing for straightforward calculation of photon counting moments including explicitly quantum effects. Unlike previous exact treatments, the present methodology involves calculation of dynamics reflecting only the modulation characteristics of the environment and quantum dynamics of an isolated chromophore separately, i.e., the complicated intermingling of chromophore quantum dynamics and the environmental modulation are suppressed via the adiabatic approximation. This leads to significant conceptual and computational simplifications. Within its regime of applicability, the present approximation reproduces exact calculations quantitatively. We demonstrate this accuracy explicitly for the case of a two-level chromophore modulated by a number of different stochastic models.
A general theory and calculation framework for the prediction of frequency-resolved single molecule photon counting statistics is presented. Expressions for the generating function of photon counts are derived, both for the case of naive "detection" based solely on photon emission from the molecule and also for experimentally realizable detection of emitted photons, and are used to explicitly calculate low-order photon-counting moments. The two cases of naive detection versus physical detection are compared to one another and it is demonstrated that the physical detection scheme resolves certain inconsistencies predicted via the naive detection approach. Applications to two different models for molecular dynamics are considered: a simple two-level system and a two-level absorber subject to spectral diffusion.
We derive the generating function for single molecule photon emission events within the context of the stochastically modulated optical Bloch equations. Statistical properties of single molecule photon counting experiments are deduced from a set of coupled differential equations only slightly more complicated than the Bloch equations themselves. This formulation allows for the study of photon bunching and antibunching within a single theoretical framework and provides a description of these behaviors that emphasizes the connection with single molecule experiments. Application is made to the spectroscopy of a chromophore coupled to a single two level system.
The use of techniques for analyzing the fluorescence photon statistics of a single molecule for modeling single-emitter dynamics is demonstrated. The photon distribution function measured in the fluorescence of a single tetra-tert-butylterrylene molecule embedded in polyisobutylene is used to devise a theoretical model for single emitters with complicated fluorescence photon statistics. Our analysis was carried out with the theoretical approach developed by Osad'ko and co-workers [J. Chem. Phys. 130, 064904 (2009); J. Phys. Chem. C 114, 10349 (2010)] for photon distribution functions. Although the experimental data were obtained at cryogenic temperature where narrow zero-phonon lines are present, the method is based on a purely statistical approach and does not require spectrally resolved data. It can also be applied to the analysis of broad fluorescence bands as measured at room temperature. Therefore, the method has prospects for revealing the quantum dynamics of single biological objects and other single quantum emitters in ambient conditions.
The statistics of photon emission from a single molecule under continuous wave excitation are considered. In particular, we study stochastic model systems where photon emission rates evolve in time with non-Markovian dynamics. Our calculations are based on the recently introduced generalized optical Bloch equation (GBE) formalism, but with numerical complications beyond those seen in previous Markovian stochastic models. A spectral representation is introduced to facilitate the numerical solution of the GBE equations for these more challenging cases.