The J- and H-bands of dye aggregate spectra: Analysis of the coherent exciton scattering (CES) approximation

The validity of the CES approximation is investigated by comparison with direct diagonalisation of a model vibronic Hamiltonian of $N$ identical monomers interacting electronically. Even for quite short aggregates (N\gtrsim 6) the CES approximation is shown to give results in agreement with direct diagonalisation, for all coupling strengths, except that of intermediate positive coupling (the H-band region). However, previously excellent agreement of CES calculations and measured spectra in the H-band region was obtained [A. Eisfeld, J. S. Briggs, Chem. Phys. 324, 376]. This is shown to arise from use of the measured monomer spectrum which includes implicitly dissipative effects not present in the model calculation

Tuning nonradiative lifetimes via molecular aggregation

We show that molecular aggregation can strongly influence the nonradiative decay (NRD) lifetime of an electronic excitation. As a demonstrative example, we consider a transition-dipole-dipole-interacting dimer whose monomers have harmonic potential energy surfaces (PESs). Depending on the position of the NRD channel ($q_{\rm nr}$), we find that the NRD lifetime ($\tau_{\rm nr}^{\rm dim}$) can exhibit a completely different dependence on the intermolecular-interaction strength. We observe that (i) for $q_{\rm nr}$ near the Franck-Condon region, $\tau_{\rm nr}^{\rm dim}$ increases with the interaction strength; (ii) for $q_{\rm nr}$ near the minimum of the monomer excited PES, the intermolecular interaction has little influence on $\tau_{\rm nr}^{\rm dim}$; (iii) for $q_{\rm nr}$ near the classical turning point of the monomer nuclear dynamics, on the other side of the minimum, $\tau_{\rm nr}^{\rm dim}$ decreases with the interaction strength. Our findings suggest design principles for molecular systems where a specific fluorescence quantum yield is desired

Anomalous strong exchange narrowing in excitonic systems

We investigate theoretically the phenomenon of exchange narrowing in the absorption spectrum of a chain of monomers, which are coupled via resonant dipole-dipole interaction. The individual (uncoupled) monomers exhibit a broad absorption line shape due to the coupling to an environment consisting of a continuum of vibrational modes. Upon increasing the interaction between the monomers, the absorption spectrum of the chain narrows. For a non-Markovian environment with a Lorentzian spectral density, we find a narrowing of the peak width (full width at half maximum (FWHM)) by a factor 1/N, where N is the number of monomers. This is much stronger than the usual 1/sqrt{N} narrowing. Furthermore it turns out that for a Markovian environment no exchange narrowing at all occurs. The relation of different measures of the width (FWHM, standard deviation) is discussed

Quantum Dynamics Simulation with Classical Oscillators

In a previous paper [J.S.Briggs and A.Eisfeld, Phys.Rev.A 85, 052111] we showed that the time-development of the complex amplitudes of N coupled quantum states can be mapped by the time development of positions and velocities of N coupled classical oscillators. Here we examine to what extent this mapping can be realised to simulate the "quantum" properties of entanglement and qubit manipulation. By working through specific examples, e.g. of quantum gate operation, we seek to illuminate quantum/classical differences which hitherto have been treated more mathematically. In addition we show that important quantum coupled phenomena, such as the Landau-Zener transition and the occurrence of Fano resonances can be simulated by classical oscillators

On the Equivalence of Quantum and Classical Coherence in Electronic Energy Transfer

To investigate the effect of quantum coherence on electronic energy transfer, which is the subject of current interest in photosynthesis, we solve the problem of transport for the simplest model of an aggregate of monomers interacting through dipole-dipole forces using both quantum and classical dynamics. We conclude that for realistic coupling strengths quantum and classical coherent transport are identical. This is demonstrated by numerical calculations for a linear chain and for the photosynthetic Fenna-Matthews-Olson (FMO) comple

Gaussian processes for choosing laser parameters for driven, dissipative Rydberg aggregates

To facilitate quantum simulation of open quantum systems at finite temperatures, an important ingredient is to achieve thermalization on a given time-scale. We consider a Rydberg aggregate (an arrangement of Rydberg atoms that interact via long-range interactions) embedded in a laser-driven atomic environment. For the smallest aggregate (two atoms), suitable laser parameters can be found by brute force scanning of the four tunable laser parameters. For more atoms, however, such parameter scans are too computationally costly. Here we apply Gaussian processes to predict the thermalization performance as a function of the laser parameters for two-atom and four-atom aggregates. These predictions perform remarkably well using just 1000 simulations, demonstrating the utility of Gaussian processes in an atomic physics setting. Using this approach, we find and present effective laser parameters for generating thermalization, the robustness of these parameters to variation, as well as different thermalization dynamics

Van-der-Waals stabilized Rydberg aggregates

Assemblies of Rydberg atoms subject to resonant dipole-dipole interactions form Frenkel excitons. We show that van-der-Waals shifts can significantly modify the exciton wave function, whenever atoms approach each other closely. As a result, attractive excitons and repulsive van-der-Waals interactions can be combined to form stable one-dimensional atom chains, akin to bound aggregates. Here the van-der-Waals shifts ensure a stronger homogeneous delocalisation of a single excitation over the whole chain, enabling it to bind up to six atoms. When brought into unstable configurations, such Rydberg aggregates allow the direct monitoring of their dissociation dynamics.Comment: 6 pages, 6 figure

Excitonic Wave Function Reconstruction from Near-Field Spectra Using Machine Learning Techniques

A general problem in quantum mechanics is the reconstruction of eigenstate wave functions from measured data. In the case of molecular aggregates, information about excitonic eigenstates is vitally important to understand their optical and transport properties. Here we show that from spatially resolved near field spectra it is possible to reconstruct the underlying delocalized aggregate eigenfunctions. Although this high-dimensional nonlinear problem defies standard numerical or analytical approaches, we have found that it can be solved using a convolutional neural network. For both one-dimensional and two-dimensional aggregates we find that the reconstruction is robust to various types of disorder and noise

Pseudomodes and the corresponding transformation of the temperature-dependent bath correlation function

In open system approaches with non-Markovian environments, the process of inserting an individual mode (denoted as "pseudomode") into the bath or extracting it from the bath is widely employed. This procedure, however, is typically performed on basis of the spectral density (SD) and does not incorporate temperature. Here, we show how the - temperature-dependent - bath correlation function (BCF) transforms in such a process. We present analytic formulae for the transformed BCF and numerically study the differences between factorizing initial state and global thermal (correlated) initial state of mode and bath, respectively. We find that in the regime of strong coupling of the mode to both system and bath, the differences in the BCFs give rise to pronounced differences in the dynamics of the system.Comment: 12 pages, 4 figure

Hierarchy of stochastic pure states for open quantum system dynamics

We derive a hierarchy of stochastic evolution equations for pure states (quantum trajectories) to efficiently solve open quantum system dynamics with non-Markovian structured environments. From this hierarchy of pure states (HOPS) the exact reduced density operator is obtained as an ensemble average. We demonstrate the power of HOPS by applying it to the Spin-Boson model, the calculation of absorption spectra of molecular aggregates and energy transfer in a photosynthetic pigment-protein complex