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Tõnu Pullerits

Publications and source records attributed to Tõnu Pullerits.

15 recordsLinked to original sources
arXiv2026

A Comparative Study of Coherent and Action-Detected 2D Electronic Spectroscopies of a Multichromophore Photosynthetic System

Coherent two-dimensional electronic spectroscopy (C-2DES) is a powerful tool for resolving excitonic structure and dynamics in light-harvesting complexes with dense energy-level manifolds. In contrast, action-detected 2DES has seen limited use on such systems, and its capacity to reveal electronic structure and dynamics remains unclear. Here we compare C-2DES and fluorescence-detected 2DES (F-2DES) on the major plant light-harvesting complex (LHCII) at 78 K. C-2DES resolves excitonic features and their spectral evolution, mapping energy-transfer pathways. F-2DES shows strong cross-peaks, but these are largely time-invariant and dominated by incoherent mixing, obscuring the dynamics. C-2DES is therefore preferred for resolving ultrafast energy transfer in light-harvesting complexes and other large interacting networks. Combined, the two measurements directly quantify the suppression of population dynamics by incoherent mixing, confirming that nearly the entire LHCII trimer network contributes. We also identify pulse-shaper nonlinearities in F-2DES as spurious features, highlighting the need for rigorous artifact suppression.

physics.chem-ph↗
arXiv2026

Franson-Interferometric Bounds on Entangled Two-Photon Absorption

Entangled photons offer quantum correlations with no classical analogue. In entangled pair two-photon absorption (ETPA), absorption rate is predicted to scale linearly rather than quadratically with photon flux, promising molecular excitation at fluxes far below the classical threshold. Reported ETPA cross sections nevertheless vary widely across experiments, largely since the observable, the differential of the transmitted flux or weak fluorescence, is difficult to separate from scattering and linear losses. We present a method which uses Franson interference to study entangled two-photon absorption through delay-dependent coincidence measurements on dye molecules. Applying the method to Rhodamine 6G, we observe a small asymmetry in the Franson interference envelope and obtain a model-derived effective cross section of approximately 2.1 E(-21) centimeter squared for Rhodamine 6G. However, the estimated systematic uncertainty does not allow a definitive ETPA assignment. Instead, the experiment establishes a quantitative bound on the ETPA response and provides a background-free benchmark for future measurements.

physics.chem-ph↗
arXiv2025

Microcavity-Enhanced Exciton Dynamics in Light-Harvesting Complexes: Insights from Redfield Theory

We investigated the exciton transfer dynamics in photosynthetic light-harvesting complex 2 (LH2) coupled to an optical microcavity. Using computational simulations based on Redfield theory, we analyzed how microcavity coupling influences energy relaxation and transfer within and between LH2 aggregates. Our results show that the exciton transfer rate between B850 rings follows a square dependence on the light-matter coupling strength, in agreement with Fermi's golden rule. Interestingly, the energy transfer rate remains almost independent of the number of LH2 complexes. This behavior is explained by the molecular components of the polaritonic wavefunction overlaps. These findings highlight the crucial role of cavity-induced polaritonic states in mediating energy transport and provide a theoretical framework for optimizing microcavity environments to enhance exciton mobility in light-harvesting systems and related photonic applications.

physics.atm-clus↗
arXiv2023

Non-Hermitian Hamiltonians for Linear and Nonlinear Optical Response: a Model for Plexcitons

In polaritons, the properties of matter are modified by mixing the molecular transitions with light modes inside a cavity. Resultant hybrid light-matter states exhibit energy level shifts, are delocalized over many molecular units and have a different excited-state potential energy landscape which leads to modified exciton dynamics. Previously, non-Hermitian Hamiltonians have been derived to describe the excited states of molecules coupled to surface plasmons (i.e. plexcitons), and these operators have been successfully used in the description of linear and third order optical response. In this article, we rigorously derive non-Hermitian Hamiltonians in the response function formalism of nonlinear spectroscopy by means of Feshbach operators, and apply them to explore spectroscopic signatures of plexcitons. In particular we analyze the optical response below and above the exceptional point that arises for matching transition energies for plasmon and molecular components, and study their decomposition using double-sided Feynman diagrams. We find a clear distinction between interference and Rabi splitting in linear spectroscopy, and a qualitative change in the symmetry of the lineshape of the nonlinear signal when crossing the exceptional. This change corresponds to one in the symmetry of the eigenvalues of the Hamiltonian. Our work presents an approach for simulating the optical response of sublevels within an electronic system, and opens new applications of nonlinear spectroscopy to examine the different regimes of the spectrum of non-Hermitian Hamiltonians.

physics.chem-ph↗
arXiv2020

Projection based adiabatic elimination of bipartite open quantum systems

Adiabatic elimination methods allow the reduction of the space dimension needed to describe systems dynamics which exhibits separation of time scale. For open quantum system, it consists in eliminating the fast part assuming it has almost instantaneously reached its steady-state and obtaining an approximation of the evolution of the slow part. These methods can be applied to eliminate a linear subspace within the system Hilbert space, or alternatively to eliminate a fast subsystems in a bipartite quantum system. In this work, we extend an adiabatic elimination method used for removing fast degrees of freedom within a open quantum system (Phys. Rev. A 2020, 101,042102) to eliminate a subsystem from an open bipartite quantum system. As an illustration, we apply our technique to a dispersively coupled two-qubit system and in the case of the open Rabi model.

quant-ph↗
arXiv2019

Adiabatic Elimination and Sub-space Evolution of Open Quantum Systems

Efficient descriptions of open quantum systems can be obtained by performing an adiabatic elimination of the fast degrees of freedom and formulating effective operators for the slow degrees of freedom in reduced dimensions. Here, we perform the construction of effective operators in frequency space, and using the final value theorem or alternatively the Keldysh theorem, we provide a correction for the trace of the density matrix which takes into account the non trace-preserving character of the evolution. We illustrate our results with two different systems, ones where the eliminated fast subspace is constituted by a continuous set of states and ones with discrete states. Furthermore, we show that the two models converge for very large dissipation and at coherent population trapping points. Our results also provide an intuitive picture of the correction to the trace of the density matrix as a detailed balance equation.

quant-ph↗
arXiv2019

Two-dimensional Fano lineshapes: Excited-state absorption contributions

Fano interferences in nanostructures are influenced by dissipation effects as well as many-body interactions. Two dimensional coherent spectroscopies have just begun to be applied to these systems where the spectroscopic signatures of a discrete-continuum structure are not known. In this article we calculate the excited-state absorption contribution for different models of higher-lying excited states. We find that the characteristic asymmetry of one-dimensional spectroscopies is recovered from the many-body contributions, and that the higher-lying excited manifolds have distorted lineshapes that are not anticipated from discrete-level Hamiltonians. We show that the SE cannot have contributions from a flat continuum of states. This work completes the Ground-State Bleach and Stimulated Emission signals that were calculated previously (Phys. Rev. B. 2016, 94, 205137). The model reproduces the observations reported for molecules on surfaces probed by 2DIR.

physics.chem-ph↗
arXiv2018

Using Fluorescence Detected Two-Dimensional Spectroscopy to Investigate Initial Exciton Delocalization Between Coupled Chromophores

Förster theory describes electronic exciton energy migration in molecular assemblies as an incoherent hopping process between donor and acceptor molecules. The rate is expressed in terms of the overlap integral between donor fluorescence and acceptor absorption spectra. Typical time scales for systems like photosynthetic antennae are on the order of a few picoseconds. Prior to transfer it is assumed that the initially excited donor molecule has equilibrated with respect to the local environment. However, upon excitation and during the equilibration phase the state of the system needs to be described by the full density matrix, including coherences between donor and acceptor states. While being intuitively clear, addressing this regime experimentally has been a challenge until the recently reported advances in Fluorescence Detected Two-Dimensional Spectroscopy (FD2DS). Here, we demonstrate using fourth order perturbation theory, the conditions for the presence of donor-acceptor coherence induced cross-peaks at zero waiting time between the first and the second pair of pulses. The approach is illustrated for a heterodimer model which facilitates an analytical solution.

physics.chem-ph↗
arXiv2017

Coherent two-dimensional spectroscopy of a Fano model

The Fano lineshape arises from the interference of two excitation pathways to reach a continuum. Its generality has resulted in a tremendous success in explaining the lineshapes of many one-dimensional spectroscopies - absorption, emission, scattering, conductance, photofragmentation - applied to very varied systems - atoms, molecules, semiconductors and metals. Unravelling a spectroscopy into a second dimension reveals the relationship between states in addition to decongesting the spectra. Femtosecond-resolved two-dimensional electronic spectroscopy (2DES) is a four-wave mixing technique that measures the time-evolution of the populations, and coherences of excited states. It has been applied extensively to the dynamics of photosynthetic units, and more recently to materials with extended band-structures. In this letter, we solve the full time-dependent third-order response, measured in 2DES, of a Fano model and give the new system parameters that become accessible.

physics.chem-ph↗
arXiv2016

Optimization Schemes for Efficient Multiple Exciton Generation and Extraction in Colloidal Quantum Dots

Multiple exciton generation is a process in which more than one electron hole pair is generated per absorbed photon. It allows us to increase the efficiency of solar energy harvesting. Experimental studies have shown the multiple exciton generation yield of 1.2 in isolated colloidal quantum dots. However real photoelectric devices require the extraction of electron hole pairs to electric contacts. We provide a systematic study of the corresponding quantum coherent processes including extraction and injection and show that a proper design of extraction and injection rates enhances the yield significantly up to values around 1.6.

cond-mat.mes-hall↗
arXiv2016

The nature of relaxation processes revealed by the action signals of phase modulated light fields

We introduce a generalized theoretical approach to study action signals induced by the absorption of two-photons from two phase modulated laser beams and subject it to experimental testing for two types of photoactive samples, solution of rhodamine 6G and GaP photodiode. In our experiment, the phases of the laser beams are modulated at the frequencies f1 and f2, respectively. The action signals, such as photoluminescence and photocurrent, which result from the absorption of two photons, are isolated at frequencies m f (f=|f1-f2|, m=0,1,2...). We demonstrate that the ratio of the amplitudes of the secondary (m=2) and the primary (m=1) signals is sensitive to the type of relaxation process taken place in the system and thus can be used for its identification. Such sensitivity originates from cumulative effects of non-equilibrated state of the system between the light pulses. When the cumulative effects are small, i.e. the relaxation time is much shorter then the laser repetition rate or the laser intensity is high enough to dominate the system behavior, the ratio achieves its reference value 1:4 (the signature of two-photon absorption). In the intermediate regimes the ratio changes rapidly with the growth of intensity from zero value in case of second order relaxation process, while it demonstrates slow monotonic decrease for linear relaxation. In the article we also determine the value of the recombination rate in a GaP photodiode by using the above approach.

physics.optics↗
arXiv2015

Isolation of coherent and incoherent nonlinear spectroscopic signals by phase modulation

We investigate the effect of phase modulation of laser beams on the coherent and incoherent non-linear signals arising from the interaction of femtosecond pulses with matter. We observe that two collinear beams, whose phases are modulated by frequencies $ϕ_1$ and $ϕ_2$, produce two second harmonic signals from non-linear crystals whose intensities at the detector are modulated at the frequencies $ϕ_2-ϕ_1$ and $2(ϕ_2-ϕ_1)$. We also observe that an incoherent action signal, such as fluorescence and photocurrent, which arises from the absorption of two photons, is modulated at the same frequencies as in the case of second harmonic generation. We present a theoretical analysis to explain our observations. These results are important to understand how phase modulation techniques can be used to isolate different field-matter interaction pathways in a non-linear process. Because the method uses modulation of the signal intensity rather than wave-vector matching to isolate different signals, it could be useful to perform multi-photon absorption studies on single molecules or nanoparticles.

physics.optics↗
arXiv2014

Exciton coupling induces vibronic hyperchromism in light-harvesting complexes

The recently suggested possibility that weak vibronic transitions can be excitonically enhanced in light-harvesting complexes is studied in detail. A vibronic exciton dimer model which includes ground state vibrations is investigated using multi-configuration time-dependent Hartree method with a parameter set typical to photosynthetic light-harvesting complexes. Absorption spectra are discussed in dependence on the Coulomb coupling, the detuning of site energies, and the number of vibrational mode. Calculations of the fluorescence spectra show that the spectral densities obtained from the low temperature fluorescence line narrowing measurements of light-harvesting systems need to be corrected for the exciton effects. For the J-aggregate configuration, as in most of the light-harvesting complexes, the true spectral density has larger amplitude than what is obtained from the measurement.

physics.chem-ph↗
arXiv2013

Generalized lock-in amplifier for precision measurement of high frequency signals

We herein formulate the concept of a generalized lock-in amplifier for the precision measurement of high frequency signals based on digital cavities. Accurate measurement of signals higher than 200 MHz using the generalized lock-in is demonstrated. The technique is compared with a traditional lock-in and its advantages and limitations are discussed. We also briefly point out how the generalized lock-in can be used for precision measurement of giga-hertz signals by using parallel processing of the digitized signals.

physics.ins-det↗