arXiv subjects

Jasper Knoester

Publications and source records attributed to Jasper Knoester.

At least 19 recordsLinked to original sources

arXiv2022

Optical Signatures of the Coupling between Excitons and Charge Transfer States in Linear Molecular Aggregates

Charge Transfer (CT) has enjoyed continuous interest due to increasing experimental control over molecular structure leading to applications in, for example, photovoltaics and hydrogen production. In this paper, we investigate the effect of CT states on the absorption spectrum of linear molecular aggregates using a scattering matrix technique that allows us to deal with arbitrarily large systems. The presented theory performs well for both strong and weak mixing of exciton and CT states, bridging the gap between previously employed methods which are applicable in only one of these limits. In experimental spectra the homogeneous linewidth is often too large to resolve all optically allowed transitions individually, resulting in a characteristic two-peak absorption spectrum in both the weak- and strong-coupling regime. Using the scattering matrix technique we examine the contributions of free and bound states in detail. We conclude that the skewness of the high-frequency peak may be used as a new way to identify the exciton-CT-state coupling strength.

physics.chem-ph↗

arXiv2021

Plasmon-assisted two-photon absorption in a semiconductor quantum dot -- metallic nanoshell composite

Tho-photon absorption holds potential for many practical applications. We theoretically investigate the onset of this phenomenon in a semiconductor quantum dot -- metallic nanoshell composite subjected to a resonant CW excitation. Two-photon absorption in this system may occur in two ways: incoherent -- due to a consecutive ground-to-one-exciton-to-biexciton transition and coherent -- due to a coherent two-photon process, involving the direct ground-to-biexciton transition in the quantum dot. The presence of the nanoshell nearby the quantum dot gives rise to two principal effects: (i) -- renormalization of the applied field amplitude and (ii) -- renormalization of the resonance frequencies and radiation relaxation rates of the quantum dot, both depending on the the quantum dot level populations. We show that in the perturbation regime, when the excitonic levels are only slightly populated, each of these factors may give rise to either suppression or enhancement of the two-photon absorption. The complicated interplay of the two determines the final effect. Beyond the perturbation regime, it is found that the two-photon absorption experiences a drastic enhancement, which occurs independently of the type of excitation, either into the one-exciton resonance or into the two-photon resonance. Other characteristic features of the two-photon absorption of the composite, emerging from the coupling between both nanoparticles, are bistability and self-oscillations.

cond-mat.mes-hall↗

arXiv2020

Exciton localization in tubular molecular aggregates: size effects and optical response

We study the exciton localization and resulting optical response for disordered tubular aggregates of optically active molecules. It has been shown previously that such tubular structures allow for excitons delocalized over more than a thousand molecules, owing to the combined effects of long-range dipole-dipole interactions and the higher-dimensional (not truly one-dimensional) nature of the aggregate. Such large delocalization sizes prompt the question to what extent in experimental systems the delocalization may still be determined by the aggregate size (diameter and length) and how this affects the aggregate's optical response and dynamics. We perform a systematic study of the size effects on the localization properties, using numerical simulations of the exciton states in a cylindrical model structure inspired by the previously derived geometry of a cylindrical aggregate of cyanine dye molecules (C8S3). To characterize the exciton localization, we calculate the participation ratio and the autocorrelation function of the exciton wave function. Also, we calculate the density of states and absorption spectrum. We find strong effects of the tube's radius on the localization and optical properties in the range of parameters relevant to experiment. In addition, surprisingly, we find that even for tubes as long as 750 nm, the localization size is limited by the tube's length for disorder values that are relevant to experimental circumstances, while observable effects of the tube's length in the absorption spectrum still occur for tube lengths up to about 150 nm. The latter may explain changes in the optical spectra observed during the aging process of bromine-substituted C8S3 aggregates. For weak disorder, the exciton wave functions exhibit a scattered, fractal-like nature, similar to the quasi-particles in two-dimensional disordered systems.

physics.chem-ph↗

arXiv2019

Interplay between Structural Hierarchy and Exciton Diffusion in Artificial Light Harvesting

Unravelling the nature of energy transport in multi-chromophoric photosynthetic complexes is essential to extract valuable design blueprints for light-harvesting applications. Long-range exciton transport in such systems is facilitated by a combination of delocalized excitation wavefunctions (excitons) and remarkable exciton diffusivities. The unambiguous identification of the exciton transport, however, is intrinsically challenging due to the system's sheer complexity. Here we address this challenge by employing a novel spectroscopic lab-on-a-chip approach: A combination of ultrafast coherent two-dimensional spectroscopy and microfluidics working in tandem with theoretical modelling. This allowed us to unveil exciton transport throughout the entire hierarchical supramolecular structure of a double-walled artificial light-harvesting complex. We show that at low exciton densities, the outer layer acts as an antenna that supplies excitons to the inner tube, while under high excitation fluences it protects the inner tube from overburning. Our findings shed light on the excitonic trajectories across different sub-units of a multi-layered supramolecular structure and underpin the great potential of artificial light-harvesting complexes for directional excitation energy transport.

physics.chem-ph↗

arXiv2018

Plasmon-assisted two-photon Rabi oscillations in a semiconductor quantum dot -- metal nanoparticle heterodimer

Tho-photon Rabi oscillations hold potential for quantum computing and quantum information processing, because during a Rabi cycle a pair of entangled photons may be created. We theoretically investigate the onset of this phenomenon in a heterodimer comprising a semiconductor quantum dot strongly coupled to a metal nanoparticle. Two-photon Rabi oscillations in this system occur due to a coherent two-photon process involving the ground-to-biexciton transition in the quantum dot. The presence of a metal nanoparticle nearby the quantum dot results in a self-action of the quantum dot via the metal nanoparticle, because the polatization state of the latter depends on the quantum state of the former. The interparticle interaction gives rise to two principal effects: (i) - enhancement of the external field amplitude and (ii) - renormalization of the quantum dot's resonance frequencies and relaxation rates of the off-diagonal density matrix elements, both depending on the populations of the quantum dot's levels. Here, we focus on the first effect, which results in interesting new features, in particular, in an increased number of Rabi cycles per pulse as compared to an isolated quantum dot and subsequent growth of the number of entangled photon pairs per pulse. We also discuss the destructive role of radiative decay of the excitonic states on two-photon Rabi oscillations for both an isolated quantum dot and a heterodimer.

quant-ph↗

arXiv2017

Unravelling coherences in the FMO complex

The idea that excitonic state (electronic) coherences are of fundamental importance to natural photosynthesis gained popularity when, a decade ago, slowly dephasing quantum beats were observed in the two-dimensional electronic spectra of the Fenna-Matthews-Olson complex at 77 K. These were assigned to quantum superpositions of excitonic states; a controversial interpretation, as the spectral linewidths suggested fast dephasing arising from strong interactions with the environment. While it has been pointed out that vibrational motion produces similar spectral signatures, concrete assignment of these coherences to distinct physical processes is still lacking. Here we revisit the coherence dynamics of the Fenna-Matthews-Olson complex using polarization-controlled two-dimensional electronic spectroscopy, supported by theoretical modelling. We show that the long-lived quantum beats originate exclusively from vibrational coherences, whereas electronic coherences dephase entirely within 240 fs even at 77 K - a timescale too short to play a significant role in light harvesting. Additionally, we demonstrate that specific vibrational coherences are excited via vibronically coupled states. The detection of vibronic coupling indicates the relevance of this phenomenon for photosynthetic energy transfer.

physics.chem-ph↗

arXiv2017

Exciton-Exciton Annihilation Is Coherently Suppressed in H-Aggregates, but Not in J-Aggregates

We theoretically demonstrate a strong dependence of the annihilation rate between (singlet) excitons on the sign of dipole-dipole couplings between molecules. For molecular H-aggregates, where this sign is positive, the phase relation of the delocalized two-exciton wavefunctions causes a destructive interference in the annihilation probability. For J-aggregates, where this sign is negative, the interference is constructive instead, as a result of which no such coherent suppression of the annihilation rate occurs. As a consequence, room temperature annihilation rates of typical H- and J-aggregates differ by a factor of ~3, while an order of magnitude difference is found for low-temperature aggregates with a low degree of disorder. These findings, which explain experimental observations, reveal a fundamental principle underlying exciton-exciton annihilation, with major implications for technological devices and experimental studies involving high excitation densities.

cond-mat.mtrl-sci↗

arXiv2016

Instabilities in the optical response of a semiconductor quantum dot - metal nanoparticle heterodimer: self - oscillations and chaos

We theoretically investigate the nonlinear optical response of a heterodimer comprising a semiconductor quantum dot strongly coupled to a metal nanoparticle. The quantum dot is considered as a three-level ladder system with ground, one-exciton, and bi-exction states. As compared to the case of a two-level quantum dot model, adding the third (bi-exciton) state produces fascinating effects in the optical response of the hybrid system. Specifically, we demonstrate that the system may exhibit picosecond and sub-picosecond self-oscillations and quasi-chaotic behaviour under {\it single}-frequency continuous wave excitation. An isolated semiconductor quantum dot does not show such features. The effects originate from competing one-exciton and bi-exciton transitions in the semiconductor quantum dot, triggered by the self-action of the quantum dot via the metal nanoparticle. The key parameter that governs the phenomena mentioned is the ratio of the self-action strength and the bi-exciton shift. The self-oscillation regime can be achieved in practice, in particular, in a heterodimer comprised of a closely spaced ZnS/ZnSe core-shell quantum dot and a spherical silver nanoparticle. The results may have applications in nanodevices for generating trains of ultrashort optical pulses.

cond-mat.mes-hall↗

arXiv2016

How two-dimensional brick layer J-aggregates differ from linear ones: excitonic properties and line broadening mechanisms

We study the excitonic coupling and homogeneous spectral line width of brick layer J-aggregate films. We begin by analysing the structural information revealed by the two-exciton states probed in two-dimensional spectra. Our first main result is that the relation between the excitonic couplings and the spectral shift in a two-dimensional structure is different (larger shift for the same nearest neighbour coupling) from that in a one-dimensional structure, which leads to an estimation of dipolar coupling in two-dimensional lattices. We next investigate the mechanisms of homogeneous broadening - population relaxation and pure dephasing - and evaluate their relative importance in linear and two-dimensional aggregates. Our second main result is that pure dephasing dominates the line width in two-dimensional systems up to a crossover temperature, which explains the linear temperature dependence of the homogeneous line width. This is directly related to the decreased density of states at the band edge when compared with linear aggregates, thus reducing the contribution of population relaxation to dephasing. Pump-probe experiments are suggested to directly measure the lifetime of the bright state and can therefore support the proposed model.

physics.chem-ph↗

arXiv2016

Quantum Diffusion on Molecular Tubes: Universal Scaling of the 1D to 2D Transition

The transport properties of disordered systems are known to depend critically on dimensionality. We study the diffusion coefficient of a quantum particle confined to a lattice on the surface of a tube, where it scales between the 1D and 2D limits. It is found that the scaling relation is universal and independent of the disorder and noise parameters, and the essential order parameter is the ratio between the localization length in 2D and the circumference of the tube. Phenomenological and quantitative expressions for transport properties as functions of disorder and noise are obtained and applied to real systems: In the natural chlorosomes found in light-harvesting bacteria the exciton transfer dynamics is predicted to be in the 2D limit, whereas a family of synthetic molecular aggregates is found to be in the homogeneous limit and is independent of dimensionality.

cond-mat.mes-hall↗

arXiv2015

Nonlinear actuation dynamics of driven Casimir oscillators with rough surfaces

At separations below 100 nm, Casimir-Lifshitz forces strongly influence the actuation dynamics of micro-electromechanical systems (MEMS) in dry vacuum conditions. For a micron size plate oscillating near a surface, which mimics a frequently used setup in experiments with MEMS, we show that the roughness of the surfaces significantly influences the qualitative dynamics of the oscillator. Via a combination of analytical and numerical methods, it is shown that surface roughness leads to a clear increase of initial conditions associated with chaotic motion, that eventually lead to stiction between the surfaces. Since stiction leads to malfunction of MEMS oscillators, our results are of central interest for the design of microdevices. Moreover, they are of significance for fundamentally motivated experiments performed with MEMS.

quant-ph↗

arXiv2015

Tailoring optical response of a hybrid comprising a quantum dimer emitter strongly coupled to a metal nanoparticle

We study theoretically the optical response of a nanohybrid comprising a symmetric quantum dimer emitter coupled to a metal nanoparticle (MNP). The interactions between the exitonic transitions in the dimer and the plasmons in the MNP lead to novel effects in the composite's input-output characteristics for the light intensity and the absorption spectrum, which we study in the linear and nonlinear regimes. We fnd that the exciton-plasmon hybridization leads to optical bistability and hysteresis for the one-exciton transition and enhancement of excitation for the two-exciton transition. The latter leads to a signifcant decrease of the field strength needed to saturate the system. In the linear regime, the absortion spectrum has a dispersive (Fano-like) line shape. The spectral position and shape of this spectrum depend on the detuning of the dimer's one-exciton resonance relative to the plasmon resonance. Upon increasing the applied field intensity to the nonlinear regime, the Fano-like singularities in the absorption spectra are smeared and they disappear due to the saturation of the dimer, which leads to the MNP dominating the spectrum. The above effects, for which we provide physical explanations, allow one to tailor the Fano-like shape of the absorption spectrum, by changing either the detuning or the input power.

cond-mat.mes-hall↗

arXiv2013

Significance of the Casimir force and surface roughness for actuation dynamics of MEMS

Using the measured optical response and surface roughness topography as inputs, we perform realistic calculations of the combined effect of Casimir and electrostatic forces on the actuation dynamics of micro-electromechanical systems (MEMS). In contrast with the expectations, roughness can influence MEMS dynamics even at distances between bodies significantly larger than the root-mean-square roughness. This effect is associated with statistically rare high asperities that can be locally close to the point of contact. It is found that, even though surface roughness appears to have a detrimental effect on the availability of stable equilibria, it ensures that those equilibria can be reached more easily than in the case of flat surfaces. Hence our findings play a principal role for the stability of microdevices such as vibration sensors, switches, and other related MEM architectures operating at distances below 100 nm.

cond-mat.mes-hall↗

arXiv2012

Roughness correction to the Casimir force at short separations: Contact distance and extreme value statistics

So far there has been no reliable method to calculate the Casimir force at separations comparable to the root-mean-square of the height fluctuations of the surfaces. Statistical analysis of rough gold samples has revealed the presence of peaks considerably higher than the root-mean-square roughness. These peaks redefine the minimum separation distance between the bodies and can be described by extreme value statistics. Here we show that the contribution of the high peaks to the Casimir force can be calculated with a pairwise additive summation, while the contribution of asperities with normal height can be evaluated perturbatively. This method provides a reliable estimate of the Casimir force at short distances, and it solves the significant, so far unexplained discrepancy between measurements of the Casimir force between rough surfaces and the results of perturbation theory. Furthermore, we illustrate the importance of our results in a technologically relevant situation.

cond-mat.mes-hall↗

arXiv2011

Roughness correction to the Casimir force beyond perturbation theory

Up to now there has been no reliable method to calculate the Casimir force when surface roughness becomes comparable with the separation between bodies. Statistical analysis of rough Au films demonstrates rare peaks with heights considerably larger than the root-mean-square (rms) roughness. These peaks define the minimal distance between rough surfaces and can be described with extreme value statistics. We show that the contributions of high peaks to the force can be calculated independently of each other while the contribution of normal roughness can be evaluated perturbatively beyond the proximity force approximation. The developed method allows a reliable force estimation for short separations. Our model explains the strong hitherto unexplained deviation from the normal Casimir scaling observed experimentally at short separations.

cond-mat.mes-hall↗

arXiv2007

Intrinsic optical bistability of thin films of linear molecular aggregates: The two-exciton approximation

We generalize our recent work on the optical bistability of thin films of molecular aggregates [J. Chem. Phys. 127, 164705 (2007); arXiv:0707.1264v1 [cond-mat.dis-nn]] by accounting for the optical transitions from the one-exciton manifold to the two-exciton manifold as well as the exciton-exciton annihilation of the two-exciton states via a high-lying molecular vibronic term. We also include the relaxation from the vibronic level back to both the one-exciton manifold and the ground state. By selecting the dominant optical transitions between the ground state, the one-exciton manifold, and the two-exciton manifold, we reduce the problem to four levels, enabling us to describe the nonlinear optical response of the film. The one- and two-exciton states are obtained by diagonalizing a Frenkel Hamiltonian with an uncorrelated on-site (diagonal) disorder. The optical dynamics is described by means of the density matrix equations coupled to the electromagnetic field in the film. We show that the one-to-two exciton transitions followed by a fast exciton-exciton annihilation promote the occurrence of bistability and reduce the switching intensity. We provide estimates of pertinent parameters for actual materials and conclude that the effect can be realized.

cond-mat.dis-nn↗

arXiv2004

Trapping time statistics and efficiency of transport of optical excitations in dendrimers

We theoretically study the trapping time distribution and the efficiency of the excitation energy transport in dendritic systems. Trapping of excitations, created at the periphery of the dendrimer, on a trap located at its core, is used as a probe of the efficiency of the energy transport across the dendrimer. The transport process is treated as incoherent hopping of excitations between nearest-neighbor dendrimer units and is described using a rate equation. We account for radiative and non-radiative decay of the excitations while diffusing across the dendrimer. We derive exact expressions for the Laplace transform of the trapping time distribution and the efficiency of trapping and analyze those for various realizations of the energy bias, number of dendrimer generations, and relative rates for decay and hopping. We show that the essential parameter that governs the trapping efficiency, is the product of the on-site excitation decay rate and the trapping time (mean first passage time) in the absence of decay.

cond-mat.mtrl-sci↗

arXiv2002

Frustrated spin model as a hard-sphere liquid

We show that one-dimensional topological objects (kinks) are natural degrees of freedom for an antiferromagnetic Ising model on a triangular lattice. Its ground states and the coexistence of spin ordering with an extensive zero-temperature entropy can be easily understood in terms of kinks forming a hard-sphere liquid. Using this picture we explain effects of quantum spin dynamics on that frustrated model, which we also study numerically.

cond-mat.stat-mech↗