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Susana F. Huelga

Publications and source records attributed to Susana F. Huelga.

At least 73 records · Page 4Linked to original sources

Fundamental limits to frequency estimation: A comprehensive microscopic perspective

We consider a scenario in which qubit-like probes are used to sense an external field that linearly affects their energy splitting. Following the frequency estimation approach in which one optimizes the state and sensing time of the probes to maximize the sensitivity, we provide a systematic study of the attainable precision under the impact of noise originating from independent bosonic baths. We invoke an explicit microscopic derivation of the probe dynamics using the spin-boson model with weak coupling of arbitrary geometry and clarify how the secular approximation leads to a phase-covariant dynamics, where the noise terms commute with the field Hamiltonian, while the inclusion of non-secular terms breaks the phase-covariance. Moreover, unless one restricts to a particular (i.e., Ohmic) spectral density of the bath modes, the noise terms may contain relevant information about the frequency to be estimated. Thus, by considering general evolutions of a single probe, we study regimes in which these two effects have a non-negligible impact on the achievable precision. We then consider baths of Ohmic spectral density yet fully accounting for the lack of phase-covariance, in order to characterize the ultimate attainable scaling of precision when $N$ probes are used in parallel. Crucially, we show that beyond the semigroup (Lindbladian) regime the Zeno limit imposing the $1/N^{3/2}$ scaling of the mean squared error, derived assuming phase-covariance, generalises to any dynamics of the probes, unless the latter are coupled to the baths in the direction perfectly transversal to the encoding---when a novel scaling of $1/N^{7/4}$ arises. As our microscopic approach covers all classes of dissipative dynamics, from semigroup to non-Markovian ones (potentially non-phase-covariant), it provides an exhaustive picture, in which all the different asymptotic scalings of precision naturally emerge.

quant-ph↗

On the theory of excitonic delocalization for robust vibronic dynamics in LH2

Nonlinear spectroscopy has revealed long-lasting oscillations in the optical response of a variety of photosynthetic complexes. Different theoretical models which involve the coherent coupling of electronic (excitonic) or electronic-vibrational (vibronic) degrees of freedom have been put forward to explain these observations. The ensuing debate concerning the relevance of either one or the other mechanism may have obscured their potential synergy. To illustrate this synergy, we quantify how the excitonic delocalization in the LH2 unit of Rhodopseudomonas Acidophila purple bacterium, leads to correlations of excitonic energy fluctuations, relevant coherent vibronic coupling and, importantly, a decrease in the excitonic dephasing rates. Combining these effects, we identify a feasible origin for the long-lasting oscillations observed in fluorescent traces from time-delayed two-pulse single molecule experiments performed on this photosynthetic complex.

q-bio.BM↗

Non-perturbative treatment of non-Markovian dynamics of open quantum systems

We identify the conditions that guarantee equivalence of the reduced dynamics of an open quantum system (OQS) for two different types of environments - one a continuous bosonic environment leading to a unitary system-environment evolution and the other a discrete-mode bosonic environment resulting in a system-mode (non-unitary) Lindbladian evolution. Assuming initial Gaussian states for the environments, we prove that the two OQS dynamics are equivalent if both the expectation values and two-time correlation functions of the environmental interaction operators are the same at all times for the two configurations. Since the numerical and analytical description of a discrete-mode environment undergoing a Lindbladian evolution is significantly more efficient than that of a continuous bosonic environment in a unitary evolution, our result represents a powerful, non-perturbative tool to describe complex and possibly highly non-Markovian dynamics. As a special application, we recover and generalize the well-known pseudomodes approach to open system dynamics.

quant-ph↗

Quantum redirection of antenna absorption to photosynthetic reaction centres

The early steps of photosynthesis involve the photo-excitation of reaction centres (RCs) and light-harvesting (LH) units. Here, we show that the --historically overlooked-- excitonic delocalisation across RC and LH pigments results in a redistribution of dipole strengths that benefits the absorption cross section of the optical bands associated with the RC of several species. While we prove that this redistribution is robust to the microscopic details of the dephasing between these units in the purple bacterium Rhodospirillum rubrum, we are able to show that the redistribution witnesses a more fragile, but persistent, coherent population dynamics which directs excitations from the LH towards the RC units under incoherent illumination and physiological conditions. Stochastic optimisation allows us to delineate clear guidelines and develop simple analytic expressions, in order to achieve directed coherent population dynamics in artificial nano-structures.

physics.bio-ph↗

Regulating the Energy Flow in a Cyanobacterial Light Harvesting Antenna Complex

Photosynthetic organisms harvest light energy, utilizing the absorption and energy transfer properties of protein-bound chromophores. Controlling the harvesting efficiency is critical for the optimal function of the photosynthetic apparatus. Here, we show that cyanobacterial light-harvesting antenna may be able to regulate the flow of energy in order to switch reversibly from efficient energy conversion to photo-protective quenching via a structural change. We isolated cyanobacterial light harvesting proteins, phycocyanin and allophycocyanin, and measured their optical properties in solution and in an aggregated-desiccated state. The results indicate that energy band structures are changed, generating a switch between two modes of operation: exciton transfer and quenching; achieved without dedicated carotenoid quenchers. This flexibility can contribute greatly to the large dynamic range of cyanobacterial light harvesting systems.

physics.bio-ph↗

Simulating spin-boson models with trapped ions

We propose a method to simulate the dynamics of spin-boson models with small crystals of trapped ions where the electronic degree of freedom of one ion is used to encode the spin while the collective vibrational degrees of freedom are employed to form an effective harmonic environment. The key idea of our approach is that a single damped mode can be used to provide a harmonic environment with Lorentzian spectral density. More complex spectral functions can be tailored by combining several individually damped modes. We propose to work with mixed-species crystals such that one species serves to encode the spin while the other species is used to cool the vibrational degrees of freedom to engineer the environment. The strength of the dissipation on the spin can be controlled by tuning the coupling between spin and vibrational degrees of freedom. In this way the dynamics of spin-boson models with macroscopic and non-Markovian environments can be simulated using only a few ions. We illustrate the approach by simulating an experiment with realistic parameters and show by computing quantitative measures that the dynamics is genuinely non-Markovian.

quant-ph↗

Open systems with error bounds: spin boson model with spectral density variations

In the study of open quantum systems, one of the most common ways to describe environmental effects on the reduced dynamics is through the spectral density. However, in many models this object cannot be computed from first principles and needs to be inferred on phenomenological grounds or fitted to experimental data. Consequently, some uncertainty regarding its form and parameters is unavoidable; this in turn calls into question the accuracy of any theoretical predictions based on a given spectral density. Here, we focus on the spin-boson model as a prototypical open quantum system, and find two error bounds on predicted expectation values in terms of the spectral density variation considered, and state a sufficient condition for the strongest one to apply. We further demonstrate an application of our result, by bounding the error brought about by the approximations involved in the Hierarchical Equations of Motion resolution method for spin-boson dynamics.

quant-ph↗

Signatures of spatially correlated noise and non-secular effects in two-dimensional electronic spectroscopy

We investigate how correlated fluctuations affect oscillatory features in rephasing and non-rephasing two-dimensional (2D) electronic spectra of a model dimer system. Based on a beating map analysis, we show that non-secular environmental couplings induced by uncorrelated fluctuations lead to oscillations centered at both cross- and diagonal-peaks in rephasing spectra as well as in non-rephasing spectra. Using an analytical approach, we provide a quantitative description of the non-secular effects in terms of the Feynman diagrams and show that the environment-induced mixing of different inter-excitonic coherences leads to oscillations in the rephasing diagonal-peaks and non-rephasing cross-peaks. We demonstrate that as correlations in the noise increase, the lifetime of oscillatory 2D signals is enhanced at rephasing cross-peaks and non-rephasing diagonal-peaks, while the other non-secular oscillatory signals are suppressed. We discuss that the asymmetry of 2D lineshapes in the beating map provides information on the degree of correlations in environmental fluctuations. Finally we investigate how the oscillatory features in 2D spectra are affected by inhomogeneous broadening.

quant-ph↗

Watching the coherent birth of polaron pairs in conjugated polymers

Organic semiconductors have the remarkable property that their optical excitation not only generates charge-neutral electron-hole pairs (excitons) but also charge-separated polaron pairs with high yield. The microscopic mechanisms underlying this charge separation have been debated for many years. Here we use ultrafast two-dimensional electronic spectroscopy to study the dynamics of polaron pair formation in a prototypical polymer thin film on a sub-20-fs time scale. We observe multi-period peak oscillations persisting for up to about 1 ps as distinct signatures of vibronic quantum coherence at room temperature. The measured two-dimensional spectra show pronounced peak splittings revealing that the elementary optical excitations of this polymer are hybridized exciton-polaron-pairs, strongly coupled to a dominant underdamped vibrational mode. Coherent vibronic coupling induces ultrafast polaron pair formation, accelerates the charge separation dynamics and makes it insensitive to disorder. These findings open up new perspectives for tailoring light-to-current conversion in organic materials.

cond-mat.mes-hall↗

Efficient simulation of non-Markovian system-environment interaction

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 illustrate the capabilities of this approach at the hand of specific examples and conclude our analysis by highlighting possible further applications of our method.

quant-ph↗

The ultimate precision limits for noisy frequency estimation

Quantum metrology protocols allow to surpass precision limits typical to classical statistics. However, in recent years, no-go theorems have been formulated, which state that typical forms of uncorrelated noise can constrain the quantum enhancement to a constant factor, and thus bound the error to the standard asymptotic scaling. In particular, that is the case of time-homogeneous (Lindbladian) dephasing and, more generally, all semigroup dynamics that include phase covariant terms, which commute with the system Hamiltonian. We show that the standard scaling can be surpassed when the dynamics is no longer ruled by a semigroup and becomes time-inhomogeneous. In this case, the ultimate precision is determined by the system short-time behaviour, which when exhibiting the natural Zeno regime leads to a non-standard asymptotic resolution. In particular, we demonstrate that the relevant noise feature dictating the precision is the violation of the semigroup property at short timescales, while non-Markovianity does not play any specific role.

quant-ph↗

Enhancing light-harvesting power with coherent vibrational interactions: a quantum heat engine picture

Recent evidence suggests that quantum effects may have functional importance in biological light-harvesting systems. Along with delocalized electronic excitations, it is now suspected that quantum coherent interactions with certain near-resonant vibrations may contribute to light-harvesting performance. However, the actual quantum advantage offered by such coherent vibrational interactions has not yet been established. We investigate a quantum design principle, whereby coherent exchange of single energy quanta between electronic and vibrational degrees of freedom can enhance a light-harvesting system's power above what is possible by thermal mechanisms alone. We present a prototype quantum heat engine which cleanly illustrates this quantum design principle, and quantify its quantum advantage using thermodynamic measures of performance. We also demonstrate the principle's relevance in parameter regimes connected to natural light-harvesting structures.

physics.chem-ph↗

Experimental detection of quantum coherent evolution through the violation of Leggett-Garg-type inequalities

We discuss the use of inequalities of the Leggett-Garg type (LGtI) to witness quantum coherence and present the first experimental violation of this type of inequalities using a light-matter interfaced system. By separately benchmarking the Markovian character of the evolution and the translational invariance of the conditional probabilities, the observed violation of a LGtI is attributed to the quantum coherent character of the process. These results provide a general method to benchmark `quantumness' when the absence of memory effects can be independently certified and confirm the persistence of quantum coherent features within systems of increasing complexity.

quant-ph↗

Optical signatures of quantum delocalization over extended domains in photosynthetic membranes

The prospect of coherent dynamics and excitonic delocalization across several light-harvesting structures in photosynthetic membranes is of considerable interest, but challenging to explore experimentally. Here we demonstrate theoretically that the excitonic delocalization across extended domains involving several light-harvesting complexes can lead to unambiguous signatures in the optical response, specifically, linear absorption spectra. We characterize, under experimentally established conditions of molecular assembly and protein-induced inhomogeneities, the optical absorption in these arrays from polarized and unpolarized excitation, and demonstrate that it can be used as a diagnostic tool to determine the coherent coupling among iso-energetic light-harvesting structures. The knowledge of these couplings would then provide further insight into the dynamical properties of transfer, such as facilitating the accurate determination of Förster rates.

physics.chem-ph↗

Vibronic origin of long-lived coherence in an artificial molecular light harvester

Natural and artificial light harvesting processes have recently gained new interest. Signatures of long lasting coherence in spectroscopic signals of biological systems have been repeatedly observed, albeit their origin is a matter of ongoing debate, as it is unclear how the loss of coherence due to interaction with the noisy environments in such systems is averted. Here we report experimental and theoretical verification of coherent exciton-vibrational (vibronic) coupling as the origin of long-lasting coherence in an artificial light harvester, a molecular J-aggregate. In this macroscopically aligned tubular system, polarization controlled 2D spectroscopy delivers an uncongested and specific optical response as an ideal foundation for an in-depth theoretical description. We derive analytical expressions that show under which general conditions vibronic coupling leads to prolonged excited-state coherence.

physics.chem-ph↗

Efficiency of quantum controlled non-Markovian thermalization

We study optimal control strategies to optimize the relaxation rate towards the fixed point of a quantum system in the presence of a non-Markovian dissipative bath. Contrary to naive expectations that suggest that memory effects might be exploited to improve optimal control effectiveness, non-Markovian effects influence the optimal strategy in a non trivial way: we present a necessary condition to be satisfied so that the effectiveness of optimal control is enhanced by non-Markovianity subject to suitable unitary controls. For illustration, we specialize our findings for the case of the dynamics of single qubit amplitude damping channels. The optimal control strategy presented here can be used to implement optimal cooling processes in quantum technologies and may have implications in quantum thermodynamics when assessing the efficiency of thermal micro-machines.

quant-ph↗

Bloch-Redfield equations for modeling light-harvesting complexes

We challenge the misconception that Bloch-Redfield equations are a less powerful tool than phenomenological Lindblad equations for modeling exciton transport in photosynthetic complexes. This view predominantly originates from an indiscriminate use of the secular approximation. We provide a detailed description of how to model both coherent oscillations and several types of noise, giving explicit examples. All issues with non-positivity are overcome by a consistent straightforward physical noise model. Herein also lies the strength of the Bloch-Redfield approach because it facilitates the analysis of noise-effects by linking them back to physical parameters of the noise environment. This includes temporal and spatial correlations and the strength and type of interaction between the noise and the system of interest. Finally we analyze a prototypical dimer system as well as a 7-site Fenna-Matthews-Olson (FMO) complex in regards to spatial correlation length of the noise, noise strength, temperature and their connection to the transfer time and transfer.

physics.bio-ph↗

Quantum Non-Markovianity: Characterization, Quantification and Detection

We present a comprehensive and up to date review on the concept of quantum non-Markovianity, a central theme in the theory of open quantum systems. We introduce the concept of quantum Markovian process as a generalization of the classical definition of Markovianity via the so-called divisibility property and relate this notion to the intuitive idea that links non-Markovianity with the persistence of memory effects. A detailed comparison with other definitions presented in the literature is provided. We then discuss several existing proposals to quantify the degree of non-Markovianity of quantum dynamics and to witness non-Markovian behavior, the latter providing sufficient conditions to detect deviations from strict Markovianity. Finally, we conclude by enumerating some timely open problems in the field and provide an outlook on possible research directions.

quant-ph↗