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Physical Review Letters

Influence of Spectral Diffusion on Single-Molecule Photon Statistics

Yiwen He, Eli Barkai

Published Aug 5, 2004• 47 citations
Publisher

Abstract

We investigate the distribution of the 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, which is valid for weak and strong excitation fields, exhibits transitions between (i) quantum sub-Poissonian and classical super-Poissonian behaviors, and (ii) fast to slow modulation limits.

DOI
10.1103/physrevlett.93.068302

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Journal of Experimental and Theoretical Physics•Jul 1, 2005•14 citations
We investigate the distribution of the 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, which is valid for weak and strong excitation fields, exhibits transitions between (i) quantum sub-Poissonian and classical super-Poissonian behaviors, and (ii) fast to slow modulation limits.
We investigate the distribution of the number of photons emitted by a single molecule undergoing a spectral diffusion process and interacting with a continuous wave laser field. The spectral diffusion is modeled based on a stochastic approach, in the spirit of the Anderson-Kubo line shape theory. Using a generating function formalism we solve the generalized optical Bloch equations and obtain an exact analytical formula for the line shape and Mandel's Q parameter. The line shape exhibits well-known behaviors, including motional narrowing when the stochastic modulation is fast and power broadening. The Mandel parameter, describing the line shape fluctuations, exhibits a transition from a quantum sub-Poissonian behavior in the fast modulation limit to a classical super-Poissonian behavior found in the slow modulation limit. Our result is applicable for weak and strong laser fields, namely, for arbitrary Rabi frequency. We show how to choose the Rabi frequency in such a way so that the quantum sub-Poissonian nature of the emission process becomes strongest. A lower bound on Q is found and simple limiting behaviors are investigated. A nontrivial behavior is obtained in the intermediate modulation limit, when the time scales for spectral diffusion and the lifetime of the excited state become similar. A comparison is made between our results and previous ones derived, based on the semiclassical generalized Wiener-Khintchine formula.
We investigate the distribution of the number of photons emitted by a single molecule undergoing a spectral diffusion process and interacting with a continuous wave laser field. The spectral diffusion is modeled based on a stochastic approach, in the spirit of the Anderson‐Kubo line shape theory. Using a generating function formalism we solve the generalized optical Bloch equations and obtain an exact analytical formula for the line shape and Mandel’s Q parameter. The line shape exhibits well-known behaviors, including motional narrowing when the stochastic modulation is fast and power broadening. The Mandel parameter, describing the line shape fluctuations, exhibits a transition from a quantum sub-Poissonian behavior in the fast modulation limit to a classical super-Poissonian behavior found in the slow modulation limit. Our result is applicable for weak and strong laser fields, namely, for arbitrary Rabi frequency. We show how to choose the Rabi frequency in such a way so that the quantum sub-Poissonian nature of the emission process becomes strongest. A lower bound on Q is found and simple limiting behaviors are investigated. A nontrivial behavior is obtained in the intermediate modulation limit, when the time scales for spectral diffusion and the lifetime of the excited state become similar. A comparison is made between our results and previous ones derived, based on the semiclassical generalized Wiener‐Khintchine formula. © 2005 American Institute of Physics. fDOI: 10.1063/1.1888388g
We present a general relation between Mandel's QQQ parameter describing variance of number of photons emitted from a single molecule and a three time correlation function describing a spectral diffusion process the molecule is undergoing. For a prototype of such a stochastic process an exact solution is found which exhibits rich types of physical behaviors.
We theoretically investigate the statistical properties of photon emission of a driven two-level single-molecule system undergoing spectral diffusion induced by nonequilibrium environmental fluctuations. Within the framework of the generating function method and the stochastic Liouville equation, we analyze the influence of the nonequilibrium characteristics of environmental fluctuations respectively governed by nonstationary Ornstein-Uhlenbeck noise and random telegraph noise on the photon counting statistics of the driven single-molecule system. In the slow modulation limit of spectral diffusion, the intensity and statistical fluctuations of photon emission depend on the environmental nonequilibrium characteristics at short time scales, whereas they become independent of the nonequilibrium characteristics of environmental fluctuations in the steady state. In the fast modulation limit of spectral diffusion, neither the line shape nor the Mandel's parameter depends on the environmental nonequilibrium characteristics owing to the rapid relaxation of environmental fluctuations. These findings not only shed light on the role of nonequilibrium environmental fluctuations in shaping the photon emission properties of single-molecule systems but also provide a basis for distinguishing between equilibrium and nonequilibrium characteristics of environmental fluctuations in experimental measurements.
A theory is formulated for time dependent fluctuations of the spectrum of a single molecule in a dynamic environment. In particular, we investigate the photon counting statistics of a single molecule undergoing a spectral diffusion process. Based on the stochastic optical Bloch equation, fluctuations are characterized by Mandel's QQQ parameter yielding the variance of number of emitted photons and the second order intensity correlation function, g(2)(t)g^{(2)}(t)g(2)(t). Using a semi-classical approach and linear response theory, we show that the QQQ parameter can be described by a three-time dipole correlation function. This approach gene ralizes the Wiener-Khintchine formula that gives the average number of fluorescent photons in terms of a one-time dipole correlation function. We classify the time ordering properties of the three-time dipole correlation function, and show that it can be represented by three different pulse shape functions similar to those used in the context of nonlinear spectroscopy. An exact solution is found for a single molecule whose absorption frequency undergoes a two state random telegraph process (i.e., the Kubo-Anderson sudden jump process.) Simple expressions are obtained from the exact solution in the slow and fast modulation regimes based on appropriate approximations for each case. In the slow modulation regime QQQ can be large even in the long time limit, while in the fast modulation regime it becomes small.
Statistics of fluorescence photons emitted by a single two-level atom interacting with a continuous wave laser field are analyzed. The photon-counting distribution is calculated for the so-called intermediate fluorescence photons, i.e., those counted during the time interval between instants at which photons are emitted. The result is a sub-Poissonian (narrower than Poisson) distribution, which agrees with experimental observations. This intermediate-photon distribution is used to calculate the average number of fluorescence photons, the second factorial moment of the photon-counting distribution, and Mandel’s Q parameter commonly used to evaluate the deviation of photon statistics from the Poisson distribution. The theoretical expressions obtained for moments of the intermediate-photon distribution are different from well-known Mandel’s formulas.