Light harvesting processes are often computationally studied from a time-dependent viewpoint, in line with ultrafast coherent spectroscopy experiments. Yet, natural processes take place in the presence of incoherent light, which induces a stationary state. Such stationary states can be described using the eigenbasis of the molecular Hamiltonian, but for realistic systems a full diagonalization is prohibitively expensive. We propose three efficient computational approaches to obtaining the stationary state that circumvent system Hamiltonian diagonalization. The connection between the incoherent perturbations, decoherence, and Kraus operators is established.
A uniform minimal model of rhodopsin photoisomerization induced by either coherent laser light or low level incoherent light (e.g. moonlight) is provided. Realistic timescales for both processes, which differ by ten orders of magnitude, are obtained. Further, a kinetic scheme involving rates for both coherent and incoherent light excitation is introduced, placing all timescales into a uniform framework.
We study the natural excitation of molecular systems, applicable to, for example, photosynthetic light-harvesting complexes, by natural incoherent light. In contrast with the conventional classical models, we show that the light need not have random character to properly represent the resultant linear excitation. Rather, thermal excitation can be interpreted as a collection of individual events resulting from the system's interaction with individual, deterministic pulsed realizations that constitute the field. The derived expressions for the individual field realizations and excitation events …
We present a theoretical study of noise-induced quantum coherences in a model three-level V-type system interacting with incoherent radiation, an important prototype for a wide range of physical systems ranging from trapped ions to biomolecules and quantum dots. By solving the quantum optical equations of motion for the V-type system, we obtain analytical expressions for the noise-induced coherences and show that they exhibit an oscillating behavior in the limit of large excited level spacing $Δ$ ($Δ/γ\gg 1$, where $γ$ is the radiative decay rate). Most remarkably, we find that in the opposite…
We formulate a comprehensive theoretical description of excitation harvesting in molecular aggregates photoexcited by weak incoherent radiation. An efficient numerical scheme that respects the continuity equation for excitation fluxes is developed to compute the nonequilibrium steady state (NESS) arising from the interplay between excitation generation, excitation relaxation, dephasing, trapping at the load, and recombination. The NESS is most conveniently described in the so-called preferred basis in which the steady-state excitonic density matrix is diagonal. The NESS properties are examined…
We present an efficient theoretical method for calculating the time evolution of the density matrix of a multilevel quantum system weakly interacting with incoherent light. The method combines the Bloch-Redfield theory with a partial secular approximation for one-photon coherences, resulting in a master equation that explicitly exposes the reliance on transition rates and the angles between transition dipole moments in the energy basis. The modified Bloch-Redfield master equation allows an unambiguous distinction between the regimes of quantum coherent vs. incoherent energy transfer under inco…
We have previously demonstrated that in the context of two-dimensional (2D) coherent electronic spectroscopy measured by phase modulation and phase-sensitive detection, an \emph{incoherent} nonlinear response, due to pairs of photoexcitations produced via linear excitation pathways, contribute to the measured signal as unexpected background [Grégoire et al., J.\ Chem.\ Phys. \textbf{147}, 114201 (2017)]. Here, we simulate the effect of such incoherent population mixing in the photocurrent signal collected from a GaAs solar cell by acting externally on the transimpedance amplifier circuit used …
The nature of excited states of open quantum systems produced by incoherent natural thermal light is analyzed based on a description of the generator of the dynamics. Natural thermal light is shown to generate long-lasting coherent dynamics because of (i) the super-Ohmic character of the radiation, and (ii) the absence of pure dephasing dynamics. In the presence of an environment, the long-lasting coherences induced by suddenly turned-on incoherent light dissipate and stationary coherences are established. As a particular application, dynamics in a subunit of the PC-645 light-harvesting comple…
We present theoretical and experimental results showing the effects of incoherent population mixing on two-dimensional (2D) coherent excitation spectra that are measured via a time-integrated population and phase-sensitive detection. The technique uses four collinear ultrashort pulses and phase modulation to acquire two-dimensional spectra by isolating specific nonlinear contributions to the photoluminescence or photocurrent excitation signal. We demonstrate that an incoherent contribution to the measured lineshape, arising from nonlinear population dynamics over the entire photoexcitation lif…
Experimental challenges and prospects for quantum-enhanced energy conversion: Stationary Fano coherence in V-type qutrits interacting with polarized incoherent radiation
Istituto Nazionale di Ottica, Consiglio Nazionale delle Ricerche (CNR-INO)（意大利国家光学研究所）；European Laboratory for Non-linear Spectroscopy (LENS), Università degli Studi di Firenze（佛罗伦萨大学非线性光谱学欧洲实验室）；Dipartimento di Fisica e Astronomia, Università degli Studi di Firenze（佛罗伦萨大学物理与天文学系）；Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche (CNR-ISC)（意大利复杂系统研究所）
The question of how quantum coherence facilitates energy transfer has been intensively debated in the scientific community. Since natural and artificial light-harvesting units operate under the stationary condition, we address this question via a non-equilibrium steady-state analysis of a molecular dimer irradiated by incoherent sunlight and then generalize the key predictions to arbitrarily-complex exciton networks. The central result of the steady-state analysis is the coherence-flux-efficiency relation:$η=c\sum_{i\neq j}F_{ij}κ_j=2c\sum_{i\neq j}J_{ij}{\rm Im}[ρ_{ij}]κ_j$ with $c$ the norma…
Light induced processes in nature occur by irradiation with slowly turned-on incoherent light. The general case of time-dependent incoherent excitation is solved here analytically for V-type systems using a newly developed master equation method. Clear evidence emerges for the disappearance of radiatively induced coherence as turn-on times of the radiation exceed characteristic system times. The latter is the case, in nature, for all relevant dynamical time scales for other than nearly degenerate energy levels. We estimate that, in the absence of non-radiative relaxation and decoherence, turn-…
In this paper we consider dynamics of a molecular system subjected to external pumping by a light source. Within a completely quantum mechanical treatment, we derive a general formula, which enables to asses effects of different light properties on the photo-induced dynamics of a molecular system. We show that once the properties of light are known in terms of certain two-point correlation function, the only information needed to reconstruct the system dynamics is the reduced evolution superoperator. The later quantity is in principle accessible through ultrafast non-linear spectroscopy. Consi…
In many important cases, the rate of excitation of a system embedded in an environment is significantly smaller than the internal system relaxation rates. An important example is that of light-induced processes under natural conditions, in which the system is excited by weak, incoherent (e.g., solar) radiation. Simulating the dynamics on the time scale of the excitation source can thus be computationally intractable. Here we describe a method for obtaining the dynamics of quantum systems without directly solving the master equation. We present an algorithm for the numerical implementation of t…
We explore the properties of steady-state Fano coherences generated in a three-level V-system continuously pumped by polarized incoherent light in the absence of coherent driving. The ratio of the stationary coherences to excited-state populations $\mathcal{C} = (1+\frac{Δ^2}{γ(r+γ)} )^{-1}$ is maximized when the excited-state splitting $Δ$ is small compared to either the spontaneous decay rate $γ$ or the incoherent pumping rate $r$. We demonstrate that an intriguing regime exists where the $\mathcal{C}$ ratio displays a maximum as a function of the dephasing rate $γ_d$. We attribute the surpr…
Transport phenomena in organic, self-assembled molecular J-aggregates have long attracted a great deal of attention due to its potential role in designing novel organic photovoltaic devices. A large number of theoretical and experimental studies have been carried out describing excitonic energy transfer in J-aggregates under the assumption that excitons are induced by a coherent laser-light source or initialized by a localized excitation on a particular chromophore. However, these assumptions may not provide an accurate description to assess the efficiency of J-aggregates, particularly as buil…
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…
The non-equilibrium stationary coherences that form in donor-acceptor systems are investigated to determine their relationship to the efficiency of energy transfer to a neighboring reaction center. It is found that the effects of asymmetry in the dimer are generally detrimental to the transfer of energy. Four types of systems are examined, arising from combinations of localized trapping, delocalized (Forster) trapping, eigenstate dephasing and site basis dephasing. In the cases of site basis dephasing the interplay between the energy gap of the excited dimer states and the environment is shown…
Oscillations in time-dependent 2D electronic spectra appear as evidence of quantum coherence in light-harvesting systems related to electronic-vibrational resonant interactions. Nature, however, takes place in a non-equilibrium steady-state, so the relevance of these arguments to the natural process is unclear. Here we examine the role of intramolecular vibrations in the non-equilibrium steady-state of photosynthetic dimers in the natural scenario of incoherent light excitation. It is found that vibrations resonant with the energy difference between exciton states do not increase the quantum y…
Excitation of molecules by incident incoherent electromagnetic radiation, such as sunlight, is described in detail and contrasted with the effect of coherent (e.g. laser) light. The nature of the quantum coherences induced by the former, relevant to transport processes in nature and in technology, is emphasized. Both equilibrium and steady state scenarios are discussed, Three examples: simple models, calcium excitation in polarized light, and the isomerization of retinal in rhodopsin are used to expose the underlying qualitative nature of the established coherences.
