In this paper, we develop a quantum-jump approach for describing the photon emission process of single fluorophore systems coupled to complex classically fluctuating reservoirs. The formalism relies on an open quantum system approach where the dynamics of the system and the reservoir fluctuations are described through a density matrix whose evolution is defined by a Lindblad rate equation. For each realization of the photon-measurement processes it is possible to define a conditional system state (stochastic density matrix) whose evolution depends on both the photon detection events and the fluctuations between the configurational states of the reservoir. In contrast to standard fluorescent systems the photon-to-photon emission process is not a renewal one, being defined by a (stochastic) waiting time distribution that in each recording event parametrically depends on the conditional state. The formalism allows calculating experimental observables such as the full hierarchy of joint probabilities associated with the time intervals between consecutive photon recording events. These results provide a powerful basis for characterizing different situations arising in single-molecule spectroscopy, such as spectral fluctuations, lifetime fluctuations and light-assisted processes.
In this paper, we develop a quantum-jump approach for describing the photon emission process of single fluorophore systems coupled to complex classically fluctuating reservoirs. The formalism relies on an open quantum system approach where the dynamics of the system and the reservoir fluctuations are described through a density matrix whose evolution is defined by a Lindblad rate equation. For each realization of the photon-measurement processes it is possible to define a conditional system state (stochastic density matrix) whose evolution depends on both the photon detection events and the fluctuations between the configurational states of the reservoir. In contrast to standard fluorescent systems the photon-to-photon emission process is not a renewal one, being defined by a (stochastic) waiting time distribution that in each recording event parametrically depends on the conditional state. The formalism allows calculating experimental observables such as the full hierarchy of joint probabilities associated with the time intervals between consecutive photon recording events. These results provide a powerful basis for characterizing different situations arising in single-molecule spectroscopy, such as spectral fluctuations, lifetime fluctuations and light-assisted processes.
In this paper, we formulate a quantum jump approach associated with single fluorescent systems whose radiative decay is defined by a Lindblad-like equation with a memory kernel. We base our results in a generalized Born–Markov approximation, which allows us to get our results from a full microscopic description. In the weak-laser-excitation regime, the photon-emission process can be described through a delay function, which in a natural way provides the basis for unravelling the dynamics in terms of a stochastic density matrix. As in the Markovian case, the stochastic dynamics consists in periods where the evolution is smooth and non-unitary, interrupted at random times where the photon-detection events produce a sudden change in the system state. The phenomenon of non-Poissonian intermittent fluorescence induced by complex environments (Budini 2006 Phys. Rev. A 73 061802) is analysed in the context of this approach.
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 nanoenvironment. 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, such as 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 one 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.
The large-deviation method can be used to study the measurement trajectories of open quantum systems. For optical arrangements this formalism allows to describe the long time properties of the (nonequilibrium) photon counting statistics in the context of a (equilibrium) thermodynamic approach defined in terms of dynamical phases and transitions between them in the trajectory space [J. P. Garrahan and I. Lesanovsky, Phys. Rev. Lett. 104, 160601 (2010)]. In this paper, we study the thermodynamic approach for fluorescent systems coupled to complex reservoirs that induce stochastic fluctuations in their dynamical parameters. In a fast modulation limit the thermodynamics corresponds to that of a Markovian two-level system. In a slow modulation limit, the thermodynamic properties are equivalent to those of a finite system that in an infinite-size limit is characterized by a first-order transition. The dynamical phases correspond to different intensity regimes, while the size of the system is measured by the transition rate of the bath fluctuations. As a function of a dimensionless intensive variable, the first and second derivatives of the thermodynamic potential develop an abrupt change and a narrow peak, respectively. Their scaling properties are consistent with a double-Gaussian probability distribution of the associated extensive variable.
An open quantum system is usually characterized by a reduced ensemble density matrix, the dynamics of which is governed by a generalized Master equation. Transforming this equation of motion into the instantaneous diagonal basis of the corresponding reduced density matrix, we can separate the coherent and incoherent part of the dynamics: The coherent dynamics is incorporated in the time development of the diagonal basis states, while the coupling to the reservoirs leads to simple rate equations. Interpreting these rate equations as a stochastic point process allows one to simulate the stochastic time evolution (random telegraph signals, ``quantum jumps'') of single-quantum systems. The diagonal representation can be considered as a generalization of the dressed-state picture of open quantum systems. Numerical simulations (``quantum Monte Carlo'') allow one to derive various dynamical properties (including correlation functions) of single-quantum systems. This concept is applied to different two- and three-level scenarios (\ensuremath{\lambda} and \ensuremath{\nu} configuration), and its limitations are discussed.
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 Q parameter yielding the variance of number of emitted photons and the second order intensity correlation function, g(2)(t). Using a semi-classical approach and linear response theory, we show that the Q 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 Q can be large even in the long time limit, while in the fast modulation regime it becomes small.
A formulation of quantum statistical ensembles in terms of probability distributions on a projective Hilbert space is developed. The combination of statistically independent systems and the reduction of a system to one of its subsystems are described by means of a tensor product of probability distributions and a reduction formula for the reduced probability distribution. Within this framework the dynamics of open quantum systems is investigated starting form a microscopic system-plus-reservoir model. Employing the Markov approximation of the classical theory of stochastic processes the short time behavior of the conditional transition probability is derived and shown to yield a differential Chapman-Kolmogorov equation. The latter has the form of a Liouville master equation for the reduced probability distribution of the open quantum system. Thus it is shown that the time-dependent wave function of an open quantum system represents a well-defined and unique stochastic process in the space of rays of the underlying Hilbert space. This stochastic process consists of a continuous time evolution generated by a nonlinear Schr\"odinger equation and a discontinuous jump process; the realizations of the processes correspond to those of the Monte Carlo wave function simulation method and to those of the jump-type evolution of the quantum trajectory method. The quantum master equation for the statistical operator is derived as the equation of motion for the two-point correlation function of the stochastic process.