In this paper, we investigate the non-Markovian dynamics of a model to mimic the excitation energy transfer (EET) between chromophores in photosynthesis systems. The numerical path integral method is used. This method includes the non-Markovian effects of the environmental affects and it does not need the perturbation approximation in solving the dynamics of systems of interest. It implies that the coherence helps the EET between chromophores through lasting the transfer time rather than enhances the transfer rate of the EET. In particular, the non-Markovian environment greatly increase the efficiency of the EET in the photosynthesis systems.
We analyze efficiency of excitation energy transfer in photosynthetic complexes in transient and stationary setting. In the transient setting the absorption process is modeled as an individual event resulting in a subsequent relaxation dynamics. In the stationary setting the absorption is a continuous stationary process, leading to the nonequilibrium steady state. We show that, as far as the efficiency is concerned, both settings can be considered to be the same, as they result in almost identical efficiency. We also show that non-Markovianity has no effect on the resulting efficiency, i.e., c…
Excitation energy transfer (EET) and electron transfer (ET) are crucially involved in photosynthetic processes. In reality, the photosynthetic reaction center constitutes an open quantum system of EET and ET, which manifests an interplay of pigments, solar light and phonon baths. So far theoretical studies have been mainly based on master equation approaches in the Markovian condition. The non-Markovian environmental effect, which may play a crucial role, has not been sufficiently considered. In this work, we propose a mixed dynamic approach to investigate this open system. The influence of ph…
In this work, we revisit the electron transfer rate theory, with particular interests in the distinct quantum solvation effect, and the characterizations of adiabatic/nonadiabatic and Markovian/non-Markovian rate processes. We first present a full account for the quantum solvation effect on the electron transfer in Debye solvents, addressed previously in J. Theore. & Comput. Chem. {\bf 5}, 685 (2006). Distinct reaction mechanisms, including the quantum solvation-induced transitions from barrier-crossing to tunneling, and from barrierless to quantum barrier-crossing rate processes, are shown in…
The non-Markovianity of the electron transfer in an oligothiophene-fullerene heterojunction described by a spin-boson model is analyzed using the time dependent decoherence canonical rates and the volume of accessible states in the Bloch sphere. The dynamical map of the reduced electronic system is computed by the hierarchical equations of motion methodology (HEOM) providing an exact dynamics. Transitory witness of non-Markovianity is linked to the bath dynamics analyzed from the HEOM auxiliary matrices. The signature of the collective bath mode detected from HEOM in each electronic state is c…
We consider population transfer in open quantum systems, which are described by quantum dynamical semigroups (QDS). Using second order perturbation theory of the Lindblad equation, we show that it depends on a weak external field only through the field's autocorrelation function (ACF), which is phase independent. Therefore, for leading order in perturbation, QDS cannot support dependence of the population transfer on the phase properties of weak fields. We examine an example of weak-field phase-dependent population transfer, and show that the phase-dependence comes from the next order in the p…
We study excitation transfer dynamics in a lattice of two level systems characterized by dynamic disorder. The diagonal and off-diagonal energy disorders arise from the coupling of system and bath. We consider both the same and the independent bath limits. In case of independent bath all diagonal and off-diagonal bath coupling elements fluctuate independently of each other and the dynamics is complicated. We obtain the time dependent population distribution by solving quantum stochastic Liouville equation (QSLE) derived by Kubo. The main result of our study is both the population transfer dyna…
Non-Markovian and non-equilibrium phonon effects are believed to be key ingredients in the energy transfer in photosynthetic complexes, especially in complexes which exhibit a regime of intermediate exciton-phonon coupling. In this work, we utilize a recently-developed measure for non-Markovianity to elucidate the exciton-phonon dynamics in terms of the information flow between electronic and vibrational degrees of freedom. We study the measure in the hierarchical equation of motion approach which captures strong system-bath coupling effects and non-equilibrium molecular reorganization. We pro…
We present a methodology for simulating multi-dimensional electronic spectra of molecular aggregates with coupling of electronic excitation to a structured environment using the stochastic non-Markovian quantum state diffusion (NMQSD) method in combination with perturbation theory for the response functions. A crucial aspect of our approach is that we propagate the NMQSD equation in a doubled system Hilbert space, but with the same noise. We demonstrate that our approach shows fast convergence with respect to the number of stochastic trajectories, providing a promising technique for numerical …
The initial stages of the evolution of an open quantum system encode the key information of its underlying dynamical correlations, which in turn can predict the trajectory at later stages. We propose a general approach based on non-Markovian dynamical maps to extract this information from the initial trajectories and compress it into non-Markovian transfer tensors. Assuming time-translational invariance, the tensors can be used to accurately and efficiently propagate the state of the system to arbitrarily long timescales. The non-Markovian Transfer Tensor Method (TTM) demonstrates the coherent…
Understanding the mechanisms of efficient and robust energy transfer in organic systems provides us with new insights for the optimal design of artificial systems. In this paper, we explore the dynamics of excitation energy transfer (EET) through a complex quantum network by a toy model consisting of three sites coupled to environments. We study how the coherent evolution and the noise-induced decoherence work together to reach efficient EET and illustrate the role of the phase factor attached to the coupling constant in the EET. By comparing the differences between the Markovian and non-Marko…
The presence of static off-diagonal disorder promotes coherent exciton transport while diffusive motion can be recovered in the presence of fluctuations in the diagonal and off-diagonal elements of the Hamiltonian. Here we study the crossover induced by correlated dynamical disorder.We uncover a novel role of the excited bath states (ExBS) in dictating quantum coherence and quantum transport in dissipative quantum systems interacting with correlated bath.We solve both analytically and numerically the temperature dependent Quantum Stochastic Liouville equation (TD-QSLE) to study temperature dep…
We show that the coherence between different bacteriochlorophyll-a (BChla) sites in the Fenna-Mathews-Olson complex is an essential ingredient for excitation energy transfer between various sites. The coherence delocalizes the excitation energy, which results in the redistribution of excitation among all the BChla sites in the steady state. We further show that the system remains partially coherent at the steady state. In our numerical simulation of the non-Markovian density matrix equation, we consider both the inhomogeneity of the protein environment and the effect of active vibronic modes.
The roles of the vibration motions played in the excitation energy transfer process are studied. It is found that a strong coherent transfer in the hybrid system emerges when the detuning between the donor and the acceptor equals the intrinsic frequency of the vibrational mode, and as a result the energy can be transferred into the acceptor much effectively. Three cases of the donor and the acceptor coupling with vibrational modes are investigated respectively. We find that the quantum interference between the two different transfer channels via the vibrational modes can affects the dynamics o…
To explain experimentally observed oscillatory dynamics of highly efficient process of excitation energy transfer (EET) in Fenna-Matthews-Olson (FMO) complex, most theoretical models assume the same local protein environment around all the bacteriochlorophyll-a (BChla) sites, contradictory to the structural analysis of FMO complex. Using different values of pigment-protein couplings for different BChla sites, measured in the adiabatic limit of electron transfer, we theoretically investigate the effect of inhomogeneous local protein environment on excitation energy transfer. By employing non-Ma…
In this work, we combine an established method for open quantum systems -- the time evolving density matrix using orthogonal polynomials algorithm (TEDOPA) -- with the transfer tensors formalism (TTM), a new tool for the analysis, compression and propagation of non-Markovian processes. This enables the investigation of previously inaccessible long-time dynamics, such as those ensuing from low temperature regimes with arbitrary, possibly highly structured, spectral densities. We briefly introduce both methods, followed by a benchmark to prove viability and combination synergies. Subsequently we…
We derive the stochastic Schrödinger equation for the system wave vector and use it to describe the excitation energy transfer dynamics in molecular aggregates. We suggest a quantum-measurement based method of estimating the excitation transfer time. Adequacy of the proposed approach is demonstrated by performing calculations on a model system. The theory is then applied to study the excitation transfer dynamics in a photosynthetic pigment-protein Fenna-Matthews-Olson (FMO) aggregate using both the Debye spectral density and the spectral density obtained from earlier molecular dynamics simulat…
In many molecular systems one encounters the situation where electronic excitations couple to a quasi-continuum of phonon modes. That continuum may be highly structured e.g. due to some weakly damped high frequency modes. To handle such a situation, an approach combining the non-Markovian quantum state diffusion (NMQSD) description of open quantum systems with an efficient but abstract approximation was recently applied to calculate energy transfer and absorption spectra of molecular aggregates [Roden, Eisfeld, Wolff, Strunz, PRL 103 (2009) 058301]. To explore the validity of the used approxim…
The influence of excited-state absorption (ESA) and two-exciton processes on a coherent population transfer with intense ultrashort chirped pulses in molecular systems in solution has been studied. An unified treatment of adiabatic rapid passage (ARP) in such systems has been developed using a three-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. We have shown that ESA has a profound effect on coherent population transfer in large molecules that necessitates a more accurate interpretation of experimental data. A simple and physically clea…
Based on a Hamiltonian that incorporates the elastic coupling between a tracer and active particles, we derive a generalized Langevin model for the non-equilibrium mechanical response of active viscoelastic biomatter. Our model accounts for the power-law viscoelastic response of the embedding polymeric network as well as for the non-equilibrium energy transfer between active and tracer particles. Our analytical expressions for the frequency-dependent response function and the positional autocorrelation function agree nicely with experimental data for red blood cells and actomyosin networks wit…
We study using the Bethe-Salpeter formalism the excitation energies of the zincbacteriochlorinbacteriochlorin dyad, a paradigmatic photosynthetic complex. In great contrast with standard timedependent density functional theory calculations with (semi)local kernels, charge transfer excitations are correctly located above the intramolecular Q-bands transitions found to be in excellent agreement with experiment. Further, the asymptotic Coulomb behavior towards the true quasiparticle gap for charge transfer excitations at long distance is correctly reproduced, showing that the present scheme allow…
In this work, we study the effects of non-Condon vibronic coupling on the quantum coherence of excitation energy transfer, via the exact dissipaton-equation-of-motion (DEOM) evaluations on excitonic model systems. Field-triggered excitation energy transfer dynamics and two dimensional coherent spectroscopy are simulated for both Condon and non-Condon vibronic couplings. Our results clearly demonstrate that the non-Condon vibronic coupling intensifies the dynamical electronic-vibrational energy transfer and enhances the total system-and-bath quantum coherence. Moreover, the hybrid bath dynamics…
By studying the lowest excitations of an exactly solvable one-dimensional molecular model, we show that components of Kohn-Sham ensembles can be used to describe charge transfers. Furthermore, we compute the approximate excitation energies obtained by using thee exact ensemble densities in the recently formulated ensemble Hartree-exchange theory [Gould and Pittalis, Phys. Rev. Lett. 119, 243001 (2017)]. Remarkably, our results show that triplet excitations are accurately reproduced across a dissociation curve in all cases tested, even in systems where ground state energies are poor due to stro…
We study the distance dependence of the rate of electronic excitation energy transfer from a dye molecule to a metal nanoparticle. Using the spherical jellium model, we evaluate the rates corresponding to the excitation of l = 1, 2, and 3 modes of the nanoparticle. Our calculation takes into account both the electron-hole pair and the plasmon excitations of the nanoparticle. The rate follows conventional R^-6 dependence at large distances while small deviations from this behavior are observed at shorter distances. Within the framework of the jellium model, it is not possible to attribute the e…
