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

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

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

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

Excitons in Molecular Aggregates with L\'evy Disorder: Anomalous Localization and Exchange Broadening of Optical Spectra

We predict the existence of exchange broadening of optical lineshapes in disordered molecular aggregates and a nonuniversal disorder scaling of the localization characteristics of the collective electronic excitations (excitons). These phenomena occur for heavy-tailed L\'evy disorder distributions with divergent second moments - distributions that play a role in many branches of physics. Our results sharply contrast with aggregate models commonly analyzed, where the second moment is finite. They bear a relevance for other types of collective excitations as well

Conical intersections in an ultracold gas

We find that energy surfaces of more than two atoms or molecules interacting via dipole-dipole po- tentials generically possess conical intersections (CIs). Typically only few atoms participate strongly in such an intersection. For the fundamental case, a circular trimer, we show how the CI affects adiabatic excitation transport via electronic decoherence or geometric phase interference. These phe- nomena may be experimentally accessible if the trimer is realized by light alkali atoms in a ring trap, whose dipole-dipole interactions are induced by off-resonant dressing with Rydberg states. Such a setup promises a direct probe of the full many-body density dynamics near a conical intersection.Comment: 4 pages, 4 figures, replacement to add archive referenc

Non-Markovian Dynamics in Ultracold Rydberg Aggregates

We propose a setup of an open quantum system in which the environment can be tuned such that either Markovian or non-Markovian system dynamics can be achieved. The implementation uses ultracold Rydberg atoms, relying on their strong long-range interactions. Our suggestion extends the features available for quantum simulators of molecular systems employing Rydberg aggregates and presents a new test bench for fundamental studies of the classification of system-environment interactions and the resulting system dynamics in open quantum systems.Comment: 13 pages, 4 figure