Quantum Stochastic Liouville Equation Research Articles

Memory effects in the efficiency control of energy transfer under incoherent light excitation in noisy environments.

Fluctuations in energy gap and coupling constants between chromophores can play an important role in absorption and energy transfer across a collection of two-level systems. In photosynthesis, light-induced quantum coherence can affect the efficiency of energy transfer to the designated "trap" state. Theoretically, the interplay between fluctuations and coherence has been studied often, employing either a Markovian or a perturbative approximation. In this study, we depart from these approaches to incorporate memory effects by using Kubo's quantum stochastic Liouville equation. We introduce the effects of decay of the created excitation (to the ground state) on the desired propagation and trapping that provides a direction of flow of the excitation. In the presence of light-induced pumping, we establish a relation between the efficiency, the mean survival time, and the correlation decay time of the bath-induced fluctuations. A decrease in the steady-state coherence during the transition from the non-Markovian regime to the Markovian limit results in a decrease in efficiency. As in the well-known Haken-Strobl model, the ratio of the square of fluctuation strength to the rate plays a critical role in determining the mechanism of energy transfer and in shaping the characteristics of the efficiency profile. We recover a connection between the transfer flux and the imaginary part of coherences in both equilibrium and excited bath states, in both correlated and uncorrelated bath models. We uncover a non-monotonic dependence of efficiency on site energy heterogeneity for both correlated and uncorrelated bath models.

A multiscale approach to coupled nuclear and electronic dynamics. I. Quantum-stochastic Liouville equation in natural internal coordinates.

Multiscale methods are powerful tools to describe large and complex systems. They are based on a hierarchical partitioning of the degrees of freedom (d.o.f.) of the system, allowing one to treat each set of d.o.f. in the most computationally efficient way. In the context of coupled nuclear and electronic dynamics, a multiscale approach would offer the opportunity to overcome the computational limits that, at present, do not allow one to treat a complex system (such as a biological macromolecule in explicit solvent) fully at the quantum mechanical level. Based on the pioneering work of Kapral and Ciccotti [R. Kapral and G. Ciccotti, J. Chem. Phys.110, 8919 (1999)], this work is intended to present a nonadiabatic theory that describes the evolution of electronic populations coupled with the dynamics of the nuclei of a molecule in a dissipative environment (condensed phases). The two elements of novelty that are here introduced are (i) the casting of the theory in the natural, internal coordinates, that are bond lengths, bond angles, and dihedral angles; (ii) the projection of those nuclear d.o.f. that can be considered at the level of a thermal bath, therefore leading to a quantum-stochastic Liouville equation. Using natural coordinates allows the description of structure and dynamics in the way chemists are used to describe molecular geometry and its changes. The projection of bath coordinates provides an important reduction of complexity and allows us to formulate the approach that can be used directly in the statistical thermodynamics description of chemical systems.

A multiscale approach to coupled nuclear and electronic dynamics. II. Exact and approximated evaluation of nonradiative transition rates.

This work follows a companion article, which will be referred to as Paper I [Campeggio et al., J. Chem. Phys. 158, 244104 (2023)] in which a quantum-stochastic Liouville equation for the description of the quantum-classical dynamics of a molecule in a dissipative bath has been formulated in curvilinear internal coordinates. In such an approach, the coordinates of the system are separated into three subsets: the quantum coordinates, the classical relevant nuclear degrees of freedom, and the classical irrelevant (bath) coordinates. The equation has been derived in natural internal coordinates, which are bond lengths, bond angles, and dihedral angles. The resulting equation needs to be parameterized. In particular, one needs to compute the potential energy surfaces, the friction tensor, and the rate constants for the nonradiative jumps among the quantum states. While standard methods exist for the calculation of energy and dissipative properties, an efficient evaluation of the transition rates needs to be developed. In this paper, an approximated treatment is introduced, which leads to a simple explicit formula with a single adjustable parameter. Such an approximated expression is compared with the exact calculation of transition rates obtained via molecular dynamics simulations. To make such a comparison possible, a simple sandbox system has been used, with two quantum states and a single internal coordinate (together with its conjugate momentum). Results show that the adjustable parameter, which is an effective decoherence time, can be parameterized from the effective relaxation times of the autocorrelation functions of the conjugated momenta of the relevant nuclear coordinates.

Excitation Energy Transfer Efficiency in Fluctuating Environments: Role of Quantum Coherence in the Presence of Memory Effects.

Several recent studies have interrogated the role of quantum coherence in affecting the transfer efficiency of an optical excitation to the designated "trap" state where the energy can be used for subsequent reactions, as in photosynthesis. However, these studies invoke a Markovian approximation for the time correlation function describing the environment-induced stochastic fluctuations. Here, we employ Kubo's quantum stochastic Liouville equation (QSLE) to include memory effects. We extend the existing QSLE scheme to introduce decay of a newly created excitation due to radiative and nonradiative channels and also by desired trapping toward the targeted chromophore. We show that the theoretical formalism based on the QSLE correctly reproduces the rate equation description in the Markovian limit, with the rate constants determined by an appropriate quantum limiting procedure. We find that under certain conditions, the efficiency of excitation transfer to the trap gains from the combined presence of quantum coherence and temporally correlated stochastic fluctuations. We work out different limiting situations in order to discover and quantify the optimum conditions for the energy transfer to the trapped state. We find that maximum energy transfer efficiency is achieved in the intermediate limit between coherent and incoherent transport.

Delocalization and Quantum Entanglement in Physical Systems.

Quantum coherence and entanglement in an extended interacting system where energy levels are nondegenerate and coupled to a dissipative environment is a common occurrence in nature, like in photosynthetic reaction systems and conjugated polymers. The temperature dependence of quantum coherence in a trimer complex (first three subunits of the Fenna-Matthews-Olson complex) is studied using a temperature-dependent quantum stochastic Liouville equation. In the non-Markovian limit, the lowering of temperature induces long-lasting quantum coherence that, in turn, leads to delocalization, whose length grows. The entanglement and coherence length determine the nature of the dynamic localization.

Environment-Assisted Quantum Coherence in Photosynthetic Complex.

Recent experiments [ Engel et al. Nature, 2007, 446, 782-786 ] revealed the existence of surprisingly long-lived quantum coherence in the noisy biological environment of the photosynthetic Fenna-Matthews-Olson (FMO) complex. Such coherence can clearly play an important role in facilitating efficient energy transfer. The occurrence of quantum coherence in quantum transport is also implicated in excitation transport processes in conjugated polymers [ Collini et al. Science, 2009, 323, 369-373 ]. Even though these systems are strongly correlated, most theoretical studies invoke a Markovian approximation where the temporal correlation of bath fluctuations is neglected. We use an elegant nonperturbative method based on Kubo's quantum stochastic Liouville equation (QSLE) to study the effects of correlated non-Markovian bath fluctuations in several different limits and find the interesting result that fluctuations not only destroy coherence but under appropriate conditions can also facilitate it. We show that temperature has the most pronounced effect in the intermediate coupling limit where it can promote transition from coherent to incoherent transfer.

Effects of dynamic disorder on exciton migration: Quantum diffusion, coherences, and energy transfer.

We study excitation transfer and migration in a one-dimensional lattice characterized by dynamic disorder. The diagonal and off-diagonal energy disorders arise from the coupling of system and bath. We consider both same bath (when baths are spatially correlated) and independent bath (when baths are completely uncorrelated) limits. In the latter case, all diagonal and off-diagonal bath coupling elements fluctuate independently of each other and the dynamics is complicated. We obtain time dependent population distribution by solving Kubo's quantum stochastic Liouville equation. In the Markovian limit, both energy transfer dynamics and mean square displacement of the exciton behave the similar way in same and independent bath cases. However, these two baths can give rise to a markedly different behavior in the non-Markovian limit. We note that previously only the same bath case has been studied in the non-Markovian limit. The other main results of our study include the following. (i) For an average, non-zero off-diagonal coupling value J, exciton migration remains coherent in same bath case even at long times while it becomes incoherent in independent bath case in the Markovian limit. (ii) Coherent transfer is manifested in an oscillatory behavior of the energy transfer dynamics accompanied by faster-than diffusive spread of the exciton from the original position. (iii) Agreement with available analytical expression of mean squared displacement is good in Markovian limit for independent bath (off-diagonal fluctuation) case but only qualitative in non-Markovian limit for which no complete analytical solution is available. (iv) We observe transition from coherent to incoherent transport in independent bath (diagonal fluctuation) case when the bath is made progressively more Markovian. We present an analytical study that shows coherence to propagate through excited bath states. (v) The correlation time of the bath plays a unique role in dictating the diffusive spread that is not anticipated in a Markovian treatment.

Quantum stochastic differential equations for boson and fermion systems—method of non-equilibrium thermo field dynamics

A unified canonical operator formalism for quantum stochastic differential equations, including the quantum stochastic Liouville equation and the quantum Langevin equation both of the Itô and the Stratonovich types, is presented within the framework of non-equilibrium thermo field dynamics (NETFD). It is performed by introducing an appropriate martingale operator in the Schrödinger and the Heisenberg representations with fermionic and bosonic Brownian motions. In order to decide the double tilde conjugation rule and the thermal state conditions for fermions, a generalization of the system consisting of a vector field and Faddeev–Popov ghosts to dissipative open situations is carried out within NETFD.

Boson and Fermion Brownian Motion

Dynamics of quantum systems which are perturbed by linear coupling to the reservoir stochastically can be studied in terms of quantum stochastic differential equations (for example, quantum stochastic Liouville equation and quantum Langevin equation). To work it out one needs definition of quantum Brownian motion. Since till very recent times only its boson version has been known, in present paper we demonstrate definition which makes possible consideration also for fermion Brownian motion.

A system of quantum stochastic differential equations in terms of non-equilibrium thermo field dynamics

Within the framework of non-equilibrium thermo field dynamics (NETFD), quantum Wiener processes at finite temperatures are constructed, and its representation space is shown to be the thermal space. After the introduction of the stochastic Shrodinger equation, a unified system of quantum stochastic differential equations, including the quantum stochastic Liouville equation and the quantum Langevin equation, is established within the quantum stochastic calculus.

QUANTUM STOCHASTIC LIOUVILLE EQUATION OF ITO TYPE

The quantum stochastic Liouville equation of Ito type is derived, for the first time, within Nonequilibrium Thermo Field Dynamics (NETFD), a unified canonical formalism for dissipative and/or stochastic fields. With the stochastic time-evolution generator of Ito type, the whole framework is inspected. Since most of the mathematical formulations of noncommutative stochastic variables are based on the equations of Ito type, the construction of the quantum stochastic Liouville equation has been highly desired. It is expected that the unified framework may provide us with a deeper insight for the mathematical foundation of quantum stochastic variables as well as for the physical one.

QUANTUM STOCHASTIC EQUATIONS FOR A NON-LINEAR DAMPED OSCILLATOR

A unified framework of stochastic differential equations for quantum systems, formulated within Non-Equilibrium Thermo Field Dynamics (NETFD), is applied to a model of non-linear damped oscillator. The quantum stochastic Liouville equation and the quantum Langevin equations (both of Ito and Stratonovich type), which are consistent with the corresponding master equation, are written down explicitly in the case of a non-conventional treatment. This solves Kubo's third problem: how one can obtain the correlations of random force operators for the Langevin equation compatible with the master equation derived by the non-conventional treatment of the damping theory.

QUANTUM STOCHASTIC HEISENBERG EQUATION

By extending the quantum stochastic Liouville equation formulated by one of the authors (T. A.) within Non-Equilibrium Thermo Field Dynamics (NETFD), it is shown that, by means of stochastic Heisenberg equation, one can construct a unified framework of stochastic differential equations for quantum systems with the quantum white noise of non-thermal ensemble. A new aspect is given to deal with the difficulties attending quantum Langevin equations.

Stochastic Liouville equation approach within non-equilibrium thermo field dynamics

The development of non-equilibrium thermo field dynamics, called NETFD in abbreviation, was started in 1983 based on the damping theory in Liouville space. It has progressed considerably since then. Especially, the structural similarity between the framework of NETFD and the framework of the usual quantum field theory was revealed. In this paper, we will show that, within the formalism of NETFD, the quantum Langevin equation and the quantum stochastic Liouville equation approach are also feasible for the construction of the quantum field theory for open systems.

Quantum Langevin equations and quantum stochastic Liouville equations

The framework of non-equilibrium thermo field dynamics (NETFD) is shown to be wide enough to take account of both the quantum Langevin equation approach and the quantum stochastic Liouville equation approach. These approaches will provide us with a complete and deeper understanding of the formalism of NETFD together with the Boltzmann equation approach and the master equation approach based on which NETFD was first constructed.