Johannes Feist: Scientific Publications
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Reply to the Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments”
Cavity-modified Chemistry: Towards Vacuum-field Catalysis
Abstract: ...In the preceding chapters, electric field effects on chemical reactivity have been extensively discussed, focusing on STM setups and enzyme catalysis among many others. Here we will focus on a rather different and only recently explored approach to manipulate chemical reactions with electric fields. With the use of resonant cavity modes hosted in Fabry–Pérot cavities for instance, as well as plasmonic modes, very recent investigations have shown modifications of chemical reactivity and dynamics, including thermal reactions and photochemistry, as well as manipulation of materials properties and non-adiabatic processes. All these works have given birth to a new field termed polaritonic chemistry due to the fact that in the so-called strong-coupling regime, polaritons become the new eigenstates of the system. These are hybrid states of light and matter that inherit properties from both constituents, providing new means to modify chemical phenomena. The aim of this chapter is two-fold: on one side, we aim to provide a general background on confined light modes and strong coupling for the non-specialised reader, and on the other, we aim to review the recent achievements of the field, paying special attention to modifications in ground-state reactivity. To this end, the chapter is organised as follows. After an introduction to settle basic concepts, we review the most relevant experimental and theoretical work in which modified chemical reactivity has been reported and conclude with the challenges faced by the field.
Photoisomerization Efficiency of a Solar Thermal Fuel in the Strong Coupling Regime
Abstract: ...Strong exciton-photon coupling is achieved when the interaction between molecules and an electromagnetic field is increased to a level where they cannot be treated as separate systems. This leads to the formation of polaritonic states and an effective rearrangement of the potential energy surfaces, which opens the possibility to modify photochemical reactions. This work investigates how the strong coupling regime is affecting the photoisomerization efficiency and thermal backconversion of a norbornadiene–quadricyclane molecular photoswitch. The quantum yield of photoisomerization shows both an excitation wavelength and exciton/photon constitution dependence. The polariton-induced decay and energy transfer processes are discussed to be the reason for this finding. Furthermore, the thermal back conversion of the system is unperturbed and the lower polariton effectively shifts the absorption onset to lower energies. The reason for the unperturbed thermal backconversion is that it occurs on the ground state, which is unaffected. This work demonstrates how strong coupling can change material properties towards higher efficiencies in applications. Importantly, the experiments illustrate that strong coupling can be used to optimize the absorption onset of the molecular photoswitch norbonadiene without affecting the back reaction from the uncoupled quadricyclane.
Multi-scale dynamics simulations of molecular polaritons: The effect of multiple cavity modes on polariton relaxation (PDF)
Abstract: ...Coupling molecules to the confined light modes of an optical cavity is showing great promise for manipulating chemical reactions. However, to fully exploit this principle and use cavities as a new tool for controlling chemistry, a complete understanding of the effects of strong light–matter coupling on molecular dynamics and reactivity is required. While quantum chemistry can provide atomistic insight into the reactivity of uncoupled molecules, the possibilities to also explore strongly coupled systems are still rather limited due to the challenges associated with an accurate description of the cavity in such calculations. Despite recent progress in introducing strong coupling effects into quantum chemistry calculations, applications are mostly restricted to single or simplified molecules in ideal lossless cavities that support a single light mode only. However, even if commonly used planar mirror micro-cavities are characterized by a fundamental mode with a frequency determined by the distance between the mirrors, the cavity energy also depends on the wave vector of the incident light rays. To account for this dependency, called cavity dispersion, in atomistic simulations of molecules in optical cavities, we have extended our multi-scale molecular dynamics model for strongly coupled molecular ensembles to include multiple confined light modes. To validate the new model, we have performed simulations of up to 512 Rhodamine molecules in red-detuned Fabry–Pérot cavities. The results of our simulations suggest that after resonant excitation into the upper polariton at a fixed wave vector, or incidence angle, the coupled cavity-molecule system rapidly decays into dark states that lack dispersion. Slower relaxation from the dark state manifold into both the upper and lower bright polaritons causes observable photo-luminescence from the molecule–cavity system along the two polariton dispersion branches that ultimately evolves toward the bottom of the lower polariton branch, in line with experimental observations. We anticipate that the more realistic cavity description in our approach will help to better understand and predict how cavities can modify molecular properties.
Few-Mode Field Quantization of Arbitrary Electromagnetic Spectral Densities (PDF)
Abstract: ...We develop a framework that provides a few-mode master equation description of the interaction between a single quantum emitter and an arbitrary electromagnetic environment. The field quantization requires only the fitting of the spectral density, obtained through classical electromagnetic simulations, to a model system involving a small number of lossy and interacting modes. We illustrate the power and validity of our approach by describing the population and electric field spatial dynamics in the spontaneous decay of an emitter placed in a complex hybrid plasmonic-photonic structure.
Molecular photodissociation enabled by ultrafast plasmon decay (PDF)
Abstract: ...We propose a strategy for enabling photodissociation of a normally photostable molecule through coupling to a nanoparticle plasmon. The large possible coupling on the single-molecule level combined with the highly lossy nature of plasmonic modes, with lifetimes on the order of femtoseconds, opens an ultrafast decay channel for the molecule. For plasmon mode frequencies below the vertical photoexcitation energy of the molecule, the difference between the excitation and emission energies is converted into vibrational energy on the molecular ground state in a Raman-like process. Under the correct conditions, this energy can be high enough to enable efficient photodissociation on the electronic ground state. We demonstrate the concept using numerical simulations of the Lindblad master equation for the hydrogen molecule in the vicinity of an aluminum nanoparticle and explore the photodissociation efficiency as a function of various system parameters.
Long-distance heat transfer between molecular systems through a hybrid plasmonic-photonic nanoresonator (PDF)
Abstract: ...We theoretically study a hybrid plasmonic-photonic cavity setup that can be used to induce and control long-distance heat transfer between molecular systems through optomechanical interactions. The structure we propose consists of two separated plasmonic nanoantennas coupled to a dielectric cavity. The hybrid modes of this resonator can combine the large optomechanical coupling of the sub-wavelength plasmonic modes with the large quality factor and delocalized character of the cavity mode that extends over a large distance (∼µm). We show that this can lead to effective long-range heat transport between molecular vibrations that can be actively controlled through an external driving laser.
Impact of Vibrational Modes in the Plasmonic Purcell Effect of Organic Molecules (PDF)
Abstract: ...By means of quantum tensor network calculations, we investigate the large Purcell effect experienced by an organic molecule placed in the vicinity of a plasmonic nanostructure. In particular, we consider a donor-π bridge-acceptor dye at the gap of two Ag nanospheres. Our theoretical approach allows for a realistic description of the continua of both molecular vibrations and optical nanocavity modes. We analyze both the ultrafast exciton dynamics in the large Purcell enhancement regime and the corresponding emission spectrum, showing that these magnitudes are not accurately represented by the simplified models used up to date. Specifically, both the two-level system model and the single vibrational mode model can only reproduce the dynamics over short time scales, whereas the Fermi’s golden rule approach accounts only for the behavior at very long times. We demonstrate that including the whole set of vibrational modes is necessary to capture most of the dynamics and the corresponding spectrum. Moreover, by disentangling the coupling of the molecule to radiative and nonradiative plasmonic modes, we also shed light into the quenching phenomenology taking place in the system.
On the SN2 reactions modified in vibrational strong coupling experiments: reaction mechanisms and vibrational mode assignments (PDF)
Abstract: ...Recent experiments have reported modified chemical reactivity under vibrational strong coupling (VSC) in microfluidic Fabry–Pérot cavities. In particular, the reaction rate of nucleophilic substitution reactions at silicon centers (SN2@Si) has been altered when a vibrational mode of the reactant was coupled to a confined light mode in the strong coupling regime. In this situation, hybrid light–matter states known as polaritons are formed and seem to be responsible for the modified chemical kinetics. These results are very encouraging for future applications of polaritonic chemistry to catalyze chemical reactions, with the ability to manipulate chemical phenomena without any external excitation of the system. Still, there is no theory capable of explaining the mechanism behind these results. In this work we address two points that are crucial for the interpretation of these experiments. Firstly, by means of electronic structure calculations we report the reaction mechanism in normal conditions of the two recently modified SN2@Si reactions, obtaining in both cases a triple-well PES where the rate-determining step is due to the Si–C and Si–O bond cleavage. Secondly, we characterize in detail the normal modes of vibration of the reactants. In the VSC experiments, reaction rates were modified only when specific vibrations of the reactants were coupled to a cavity mode. We find that these vibrations are highly mixed among the different fragments of the reactants leading to a completely new assignment of the IR peaks coupled to cavity modes in the original experimental works. Our results are fundamental for the interpretation of the VSC experiments given that in the absence of a theory explaining these results, the current phenomenological understanding relies on the assignment of the character of the vibrational IR peaks.
Theory of Energy Transfer in Organic Nanocrystals (PDF)
Abstract: ...Recent experiments have shown that highly efficient energy transfer can take place in organic nanocrystals at extremely low acceptor densities. This striking phenomenon has been ascribed to the formation of exciton polaritons thanks to the photon confinement provided by the crystal itself. An alternative theoretical model that accurately reproduces fluorescence lifetime and spectrum measurements in these systems without such an assumption is proposed. The approach treats molecule–photon interactions in the weak-coupling regime, and describes the donor and acceptor population dynamics by means of rate equations with parameters extracted from electromagnetic simulations. The physical insight and predictive value of this model also enables the authors to propose nanocrystal configurations in which acceptor emission dominates the fluorescence spectrum at densities orders of magnitude lower than the experimental ones.
Macroscopic QED for quantum nanophotonics: emitter-centered modes as a minimal basis for multiemitter problems (PDF)
Abstract: ...We present an overview of the framework of macroscopic quantum electrodynamics from a quantum nanophotonics perspective. Particularly, we focus our attention on three aspects of the theory that are crucial for the description of quantum optical phenomena in nanophotonic structures. First, we review the light–matter interaction Hamiltonian itself, with special emphasis on its gauge independence and the minimal and multipolar coupling schemes. Second, we discuss the treatment of the external pumping of quantum optical systems by classical electromagnetic fields. Third, we introduce an exact, complete, and minimal basis for the field quantization in multiemitter configurations, which is based on the so-called emitter-centered modes. Finally, we illustrate this quantization approach in a particular hybrid metallodielectric geometry: two quantum emitters placed in the vicinity of a dimer of Ag nanospheres embedded in a SiN microdisk.
Photoprotecting Uracil by Coupling with Lossy Nanocavities (PDF)
Abstract: ...We analyze how the photorelaxation dynamics of a molecule can be controlled by modifying its electromagnetic environment using a nanocavity mode. In particular, we consider the photorelaxation of the RNA nucleobase uracil, which is the natural mechanism to prevent photodamage. In our theoretical work, we identify the operative conditions in which strong coupling with the cavity mode can open an efficient photoprotective channel, resulting in a relaxation dynamics twice as fast as the natural one. We rely on a state-of-the-art chemically detailed molecular model and a non-Hermitian Hamiltonian propagation approach to perform full-quantum simulations of the system dissipative dynamics. By focusing on the photon decay, our analysis unveils the active role played by cavity-induced dissipative processes in modifying chemical reaction rates, in the context of molecular polaritonics. Remarkably, we find that the photorelaxation efficiency is maximized when an optimal trade-off between light–matter coupling strength and photon decay rate is satisfied. This result is in contrast with the common intuition that increasing the quality factor of nanocavities and plasmonic devices improves their performance. Finally, we use a detailed model of a metal nanoparticle to show that the speedup of the uracil relaxation could be observed via coupling with a nanosphere pseudomode, without requiring the implementation of complex nanophotonic structures.
Polaritonic molecular clock for all-optical ultrafast imaging of wavepacket dynamics without probe pulses (PDF)
Abstract: ...Conventional approaches to probing ultrafast molecular dynamics rely on the use of synchronized laser pulses with a well-defined time delay. Typically, a pump pulse excites a molecular wavepacket. A subsequent probe pulse can then dissociate or ionize the molecule, and measurement of the molecular fragments provides information about where the wavepacket was for each time delay. Here, we propose to exploit the ultrafast nuclear-position-dependent emission obtained due to large light–matter coupling in plasmonic nanocavities to image wavepacket dynamics using only a single pump pulse. We show that the time-resolved emission from the cavity provides information about when the wavepacket passes a given region in nuclear configuration space. This approach can image both cavity-modified dynamics on polaritonic (hybrid light–matter) potentials in the strong light–matter coupling regime and bare-molecule dynamics in the intermediate coupling regime of large Purcell enhancements, and provides a route towards ultrafast molecular spectroscopy with plasmonic nanocavities.
Cumulant expansion for the treatment of light-matter interactions in arbitrary material structures (PDF)
Abstract: ...Strong coupling of quantum emitters with confined electromagnetic modes of nanophotonic structures may be used to change optical, chemical, and transport properties of materials, with significant theoretical effort invested toward a better understanding of this phenomenon. However, a full theoretical description of both matter and light is an extremely challenging task. Typical theoretical approaches simplify the description of the photonic environment by describing it as a single mode or few modes. While this approximation is accurate in some cases, it breaks down strongly in complex environments, such as within plasmonic nanocavities, and the electromagnetic environment must be fully taken into account. This requires the quantum description of a continuum of bosonic modes, a problem that is computationally hard. We here investigate a compromise where the quantum character of light is taken into account at modest computational cost. To do so, we focus on a quantum emitter that interacts with an arbitrary photonic spectral density and employ the cumulant, or cluster, expansion method to the Heisenberg equations of motion up to first, second, and third order. We benchmark the method by comparing it with exact solutions for specific situations and show that it can accurately represent dynamics for many parameter ranges.
Tracking Polariton Relaxation with Multiscale Molecular Dynamics Simulations (PDF)
Abstract: ...When photoactive molecules interact strongly with confined light modes in optical cavities, new hybrid light–matter states form. They are known as polaritons and correspond to coherent superpositions of excitations of the molecules and of the cavity photon. The polariton energies and thus potential energy surfaces are changed with respect to the bare molecules, such that polariton formation is considered a promising paradigm for controlling photochemical reactions. To effectively manipulate photochemistry with confined light, the molecules need to remain in the polaritonic state long enough for the reaction on the modified potential energy surface to take place. To understand what determines this lifetime, we have performed atomistic molecular dynamics simulations of room-temperature ensembles of rhodamine chromophores strongly coupled to a single confined light mode with a 15 fs lifetime. We investigated three popular experimental scenarios and followed the relaxation after optically pumping (i) the lower polariton, (ii) the upper polariton, or (iii) uncoupled molecular states. The results of the simulations suggest that the lifetimes of the optically accessible lower and upper polaritons are limited by (i) ultrafast photoemission due to the low cavity lifetime and (ii) reversible population transfer into the “dark” state manifold. Dark states are superpositions of molecular excitations but with much smaller contributions from the cavity photon, decreasing their emission rates and hence increasing their lifetimes. We find that population transfer between polaritonic modes and dark states is determined by the overlap between the polaritonic and molecular absorption spectra. Importantly, excitation can also be transferred ”upward” from the lower polariton into the dark-state reservoir due to the broad absorption spectra of the chromophores, contrary to the common conception of these processes as a ”one-way” relaxation from the dark states down to the lower polariton. Our results thus suggest that polaritonic chemistry relying on modified dynamics taking place within the lower polariton manifold requires cavities with sufficiently long lifetimes and, at the same time, strong light–matter coupling strengths to prevent the back-transfer of excitation into the dark states.
Optomechanical heat transfer between molecules in a nanoplasmonic cavity (PDF)
Abstract: ...We explore whether localized surface plasmon polariton modes can transfer heat between molecules placed in the hot spot of a nanoplasmonic cavity through optomechanical interaction with the molecular vibrations. We demonstrate that external driving of the plasmon resonance indeed induces an effective molecule-molecule interaction corresponding to a heat transfer mechanism that can even be more effective in cooling the hotter molecule than its heating due to the vibrational pumping by the plasmon. This mechanism allows us to actively control the rate of heat flow between molecules through the intensity and frequency of the driving laser.
Cavity-Modified Exciton Dynamics in Photosynthetic Units (PDF)
Abstract: ...Recently, exciton-photon strong coupling has been proposed as a means to control and enhance energy transfer in ensembles of organic molecules. Here, we demonstrate that the exciton dynamics in an archetypal purple bacterial photosynthetic unit, composed of six LH2 antennas surrounding a single LH1 complex, is greatly modified by its interaction with an optical cavity. We develop a Bloch-Redfield master equation approach that accounts for the interplay between the B800 and B850 bacteriochlorophyll molecules within each LH2 antenna, as well as their interactions with the central LH1 complex. Using a realistic parametrization of both the photosynthetic unit and optical cavity, we investigate the formation of polaritons in the system, revealing that these can be tuned to accelerate its exciton dynamics by 3 orders of magnitude. This yields a significant occupation of the LH1 complex, the stage immediately prior to the reaction center, with only a few-femtosecond delay after the initial excitation of the LH2 B800 pigments. Our theoretical findings unveil polaritonic phenomena as a promising route for the characterization, tailoring, and optimization of light-harvesting mechanisms in natural and artificial photosynthetic processes.
Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity (PDF)
Abstract: ...Here, we present a fundamental study on how the ground-state chemical reactivity of a single molecule can be modified in a QED scenario, i.e., when it is placed inside a nanoscale cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a model system for the molecule (Shin-Metiu model) in which nuclear, electronic, and photonic degrees of freedom are treated on the same footing. This simplified model allows the comparison of exact quantum reaction rate calculations with predictions emerging from transition state theory based on the cavity Born-Oppenheimer approach. We demonstrate that QED effects are indeed able to significantly modify activation barriers in chemical reactions and, as a consequence, reaction rates. The critical physical parameter controlling this effect is the permanent dipole of the molecule and how this magnitude changes along the reaction coordinate. We show that the effective coupling can lead to significant single-molecule energy shifts in an experimentally available nanoparticle-on-mirror cavity. We then apply the validated theory to a realistic case (internal rotation in the 1,2-dichloroethane molecule), showing how reactions can be inhibited or catalyzed depending on the profile of the molecular dipole. Furthermore, we discuss the absence of resonance effects in the present scenario, which can be understood through its connection to Casimir-Polder forces. Finally, we treat the case of many-molecule strong coupling and find collective modifications of reaction rates if the molecular permanent dipole moments are oriented with respect to the cavity field.
Strong coupling between weakly guided semiconductor nanowire modes and an organic dye (PDF)
Abstract: ...The light-matter coupling between electromagnetic modes guided by a semiconductor nanowire and excitonic states of molecules localized in its surrounding media is studied from both classical and quantum perspectives, with the aim of describing the strong-coupling regime. Weakly guided modes (bare photonic modes) are found through a classical analysis, identifying those lowest-order modes presenting large electromagnetic fields spreading outside the nanowire while preserving their robust guided behavior. Experimental fits of the dielectric permittivity of an organic dye that exhibits excitonic states are used for realistic scenarios. A quantum model properly confirms through an avoided mode crossing that the strong-coupling regime can be achieved for this configuration, leading to Rabi splitting values above 100 meV. In addition, it is shown that the coupling strength depends on the fraction of energy spread outside the nanowire, rather than on the mode field localization. These results open up a new avenue towards strong-coupling phenomenology involving propagating modes in nonabsorbing media.
Plasmonic Nanocavities Enable Self-Induced Electrostatic Catalysis (PDF)
Abstract: ...The potential of strong interactions between light and matter remains to be further explored within a chemical context. Towards this end herein we study the electromagnetic interaction between molecules and plasmonic nanocavities. By means of electronic structure calculations, we show that self-induced catalysis emerges without any external stimuli through the interaction of the molecular permanent and fluctuating dipole moments with the plasmonic cavity modes. We also exploit this scheme to modify the transition temperature T1/2 of spin-crossover complexes as an example of how strong light–matter interactions can ultimately be used to control a materials responses.
Polarization tagging of two-photon double ionization by elliptically polarized XUV pulses (PDF)
Abstract: ...We explore the influence of elliptical polarization on the (non)sequential two-photon double ionization of atomic helium with ultrashort extreme ultraviolet (XUV) light fields using time-dependent full ab initio simulations. The energy and angular distributions of photoelectrons are found to be strongly dependent on the ellipticity. The correlation minimum in the joint angular distribution becomes more prominently visible with increasing ellipticity. In a pump-probe sequence of two subsequent XUV pulses with varying ellipticities, polarization tagging allows us to discriminate between sequential and nonsequential photoionization. This clear separation demonstrates the potential of elliptically polarized XUV fields for improved control of electronic emission processes.
Tensor Network Simulation of Non-Markovian Dynamics in Organic Polaritons (PDF)
Abstract: ...We calculate the exact many-body time dynamics of polaritonic states supported by an optical cavity filled with organic molecules. Optical, vibrational, and radiative processes are treated on an equal footing employing the time-dependent variational matrix product states algorithm. We demonstrate signatures of non-Markovian vibronic dynamics and its fingerprints in the far-field photon emission spectrum at arbitrary light-matter interaction scales, ranging from the weak to the strong coupling regimes. We analyze both the single- and many-molecule cases, showing the crucial role played by the collective motion of molecular nuclei and dark states in determining the polariton dynamics and the subsequent photon emission.
A pump–probe scheme with a single chirped pulse to image electron and nuclear dynamics in molecules (PDF)
Abstract: ...A single chirped few-femtosecond pulse can be used to control and image coupled electron-nuclear dynamics. Using full ab initio simulations of the simplest molecule, H2+, as a prototype target, we show that for intermediate values of the chirp, interference between sequential and direct contributions enables significant control over ionization yields, even when taking into account the effective decoherence introduced by nuclear motion and the presence of an electronic continuum. For larger values of the chirp, the single chirped pulse reproduces a classical pump-probe setup, with the chirp parameter mapping an effective time delay between the pumping and probing frequencies of the pulse. After demonstrating this numerically, we present a full analytical solution for the two-photon ionization amplitudes that provides an intuitive analogy between the molecular dynamics induced by a single chirped pulse and a traditional pump-probe setup.
Tensor network simulation of polaron-polaritons in organic microcavities (PDF)
Abstract: ...In the regime of strong coupling between molecular excitons and confined optical modes, the intramolecular degrees of freedom are profoundly affected, leading to a reduced vibrational dressing of polaritons compared to bare electronically excited states. However, existing models only describe a single vibrational mode in each molecule, while actual molecules possess a large number of vibrational degrees of freedom and additionally interact with a continuous bath of phononic modes in the host medium in typical experiments. In this work, we investigate a small ensemble of molecules with an arbitrary number of vibrational degrees of freedom under strong coupling to a microcavity mode. We demonstrate that reduced vibrational dressing is still present in this case, and show that the influence of the phononic environment on most electronic and photonic observables in the lowest excited state can be predicted from just two collective parameters of the vibrational modes. Besides, we explore vibrational features that can be addressed exclusively by our extended model and could be experimentally tested. Our findings indicate that vibronic coupling is more efficiently suppressed for environments characterized by low-frequency (sub-Ohmic) modes.
Exploring the Limits of Super-Planckian Far-Field Radiative Heat Transfer Using 2D Materials (PDF)
Abstract: ...Very recently it has been predicted that the far-field radiative heat transfer between two macroscopic systems can largely overcome the limit set by Planck’s law if one of their dimensions becomes much smaller than the thermal wavelength (λTh ≈ 10 μm at room temperature). To explore the ultimate limit of the far-field violation of Planck’s law, here we present a theoretical study of the radiative heat transfer between two-dimensional (2D) materials. We show that the far-field thermal radiation exchanged by two coplanar systems with a one-atom-thick geometrical cross section can be more than 7 orders of magnitude larger than the theoretical limit set by Planck’s law for blackbodies and can be comparable to the heat transfer of two parallel sheets at the same distance. In particular, we illustrate this phenomenon with different materials such as graphene, where the radiation can also be tuned by a external gate, and single-layer black phosphorus. In both cases the far-field radiative heat transfer is dominated by TE-polarized guiding modes, and surface plasmons play no role. Our predictions provide a new insight into the thermal radiation exchange mechanisms between 2D materials.
Photon statistics in collective strong coupling: Nanocavities and microcavities (PDF)
Abstract: ...There exists a growing interest in the properties of the light generated by hybrid systems involving a mesoscopic number of emitters as a means of providing macroscopic quantum light sources. In this work, the quantum correlations of the light emitted by a collection of emitters coupled to a generic optical cavity are studied theoretically using an effective Hamiltonian approach. Starting from the single-emitter level, we analyze the persistence of photon antibunching as the ensemble size increases. Not only is the photon blockade effect identifiable, but photon antibunching originated from destructive interference processes, the so-called unconventional antibunching, is also present. We study the dependence of these two types of negative correlations on the spectral detuning between cavity and emitters, as well as its evolution as the time delay between photon detections increases. Throughout this work, the performance of plasmonic nanocavities and dielectric microcavities is compared: despite the distinct energy scales and the differences introduced by their respectively open and closed character, the bunching and antibunching phenomenology presents remarkable similarities in both types of cavities.
Electron correlations in the antiproton energy-loss distribution in He (PDF)
Abstract: ...We present ab initio calculations of the electronic differential energy-transfer cross sections for antiprotons with energies between 3 keV and 1 MeV interacting with helium. By comparison with simulations employing the mean-field description based on the single-active electron approximation we are able to identify electron correlation effects in the stopping and straggling cross sections. Most remarkably, we find that straggling exceeds the celebrated Bohr straggling limit when correlated shake-up processes are included.
Organic polaritons enable local vibrations to drive long-range energy transfer (PDF)
Abstract: ...Long-range energy transfer in organic molecules has been experimentally obtained by strongly coupling their electronic excitations to a confined electromagnetic cavity mode. Here, we shed light into the polariton-mediated mechanism behind this process for different configurations: donor and acceptor molecules either intermixed or physically separated.We numerically address the phenomenon by means of Bloch-Redfield theory, which allows us to reproduce the effect of complex vibrational reservoirs characteristic of organic molecules. Our findings reveal the key role played by the middle polariton as the nonlocal intermediary in the transmission of excitations from donor to acceptor molecules.We also provide analytical insights on the key physical magnitudes that help to optimize the efficiency of the long-range energy transfer.
Reply to the Comment on ‘Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode’ (2015 New J. Phys. 17 053040) (PDF)
Polaritonic Chemistry with Organic Molecules (PDF)
Abstract: ...We present an overview of the general concepts of polaritonic chemistry with organic molecules, i.e., the manipulation of chemical structure that can be achieved through strong coupling between confined light modes and organic molecules. Strong coupling and the associated formation of polaritons, hybrid light-matter excitations, leads to energy shifts in such systems that can amount to a large fraction of the uncoupled transition energy. This has recently been shown to significantly alter the chemical structure of the coupled molecules, which opens the possibility to manipulate and control reactions. We discuss the current state of theory for describing these changes and present several applications, with a particular focus on the collective effects observed when many molecules are involved in strong coupling.
Dispersion Anisotropy of Plasmon–Exciton–Polaritons in Lattices of Metallic Nanoparticles (PDF)
Abstract: ...When the electromagnetic modes supported by plasmonic-based cavities interact strongly with molecules located within the cavity, new hybrid states known as plasmon-exciton-polaritons (PEPs) are formed. The properties of PEPs, such as group velocity, effective mass and lifetime, depend on the dispersive and spectral characteristics of the optical modes underlying the strong coupling. In this work, we focus on lattice modes supported by rectangular arrays of plasmonic nanoparticles known as surface lattice resonances (SLRs). We show that SLRs arising from different in-plane diffraction orders in the lattice can couple with the molecular excitons leading to PEPs with distinct dispersions, and thus different group velocities. These results illustrate the possibility of tailoring the transport of PEPs through the design of lattices of plasmonic particles.
Super-Planckian far-field radiative heat transfer (PDF)
Abstract: ...We present here a theoretical analysis that demonstrates that the far-field radiative heat transfer between objects with dimensions smaller than the thermal wavelength can overcome the Planckian limit by orders of magnitude. To guide the search for super-Planckian far-field radiative heat transfer, we make use of the theory of fluctuational electrodynamics and derive a relation between the far-field radiative heat transfer and the directional absorption efficiency of the objects involved. Guided by this relation, and making use of state-of-the-art numerical simulations, we show that the far-field radiative heat transfer between highly anisotropic objects can largely overcome the black-body limit when some of their dimensions are smaller than the thermal wavelength. In particular, we illustrate this phenomenon in the case of suspended pads made of polar dielectrics like SiN or SiO2 . These structures are widely used to measure the thermal transport through nanowires and low-dimensional systems and can be employed to test our predictions. Our work illustrates the dramatic failure of the classical theory to predict the far-field radiative heat transfer between micro- and nanodevices.
Enhancing photon correlations through plasmonic strong coupling (PDF)
Abstract: ...There is an increasing scientific and technological interest in the design and implementation of nanoscale sources of quantum light. Here, we investigate the quantum statistics of the light scattered from a plasmonic nanocavity coupled to a mesoscopic ensemble of emitters under low coherent pumping. We present an analytical description of the intensity correlations taking place in these systems and unveil the fingerprint of plasmon-exciton-polaritons in them. Our findings reveal that plasmonic cavities are able to retain and enhance excitonic nonlinearities, even when the number of emitters is large. This makes plasmonic strong coupling a promising route for generating nonclassical light beyond the single-emitter level.
Long-distance operator for energy transfer (PDF)
Abstract: ...Nonradiative energy transfer is a ubiquitous phenomenon in nature. Photosynthesis begins with light harvesting, where pigment-protein complexes transform sunlight into excitations, usually called excitons, within the molecules. Excitons are formed by an excited electron and the positively charged hole that is left in the ground state. In photosynthesis, the energy of this exciton is finally transferred to the reaction center, where a charge separation process provides chemical energy for plants, algae, and bacteria. Human-made organic photovoltaic cells try to mimic this natural process, and it is the transport of the excitons after light absorption that determines the efficiency of the cell. In organic materials, energy transfer is governed by short-range dipole-dipole interactions through the process of Förster resonance energy transfer (FRET), whose spatial range is limited to distances less than 10 nm. Recent work by Zhong et al. shows how this range can be extended to distances larger than 100 nm by taking advantage of a quantum electrodynamics (QED) phenomenon called strong coupling.
Many-Molecule Reaction Triggered by a Single Photon in Polaritonic Chemistry (PDF)
Abstract: ...The second law of photochemistry states that in most cases, no more than one molecule is activated for an excited-state reaction for each photon absorbed by a collection of molecules. In this work, we demonstrate that it is possible to trigger a many-molecule reaction using only one photon by strongly coupling the molecular ensemble to a confined light mode. The collective nature of the resulting hybrid states of the system (the so-called polaritons) leads to the formation of a polaritonic "supermolecule" involving the degrees of freedom of all molecules, opening a reaction path on which all involved molecules undergo a chemical transformation. We theoretically investigate the system conditions for this effect to take place and be enhanced.
Multiscale Molecular Dynamics Simulations of Polaritonic Chemistry (PDF)
Abstract: ...When photoactive molecules interact strongly with confined light modes as found in plasmonic structures or optical cavities, new hybrid light-matter states can form, the so-called polaritons. These polaritons are coherent superpositions (in the quantum mechanical sense) of excitations of the molecules and of the cavity photon or surface plasmon. Recent experimental and theoretical works suggest that access to these polaritons in cavities could provide a totally new and attractive paradigm for controlling chemical reactions that falls in between traditional chemical catalysis and coherent laser control. However, designing cavity parameters to control chemistry requires a theoretical model with which the effect of the light-matter coupling on the molecular dynamics can be predicted accurately. Here we present a multiscale quantum mechanics/molecular mechanics (QM/ MM) molecular dynamics simulation model for photoactive molecules that are strongly coupled to confined light in optical cavities or surface plasmons. Using this model we have performed simulations with up to 1600 Rhodamine molecules in a cavity. The results of these simulations reveal that the contributions of the molecules to the polariton are time-dependent due to thermal fluctuations that break symmetry. Furthermore, the simulations suggest that in addition to the cavity quality factor, also the Stokes shift and number of molecules control the lifetime of the polariton. Because large numbers of molecules interacting with confined light can now be simulated in atomic detail, we anticipate that our method will lead to a better understanding of the effects of strong coupling on chemical reactivity. Ultimately the method may even be used to systematically design cavities to control photochemistry.
Imaging ultrafast molecular wave packets with a single chirped UV pulse (PDF)
Abstract: ...We show how to emulate a conventional pump-probe scheme using a single frequency-chirped ultrashort UV pulse to obtain a time-resolved image of molecular ultrafast dynamics. The chirp introduces a spectral phase in time that encodes the delay between the pump and the probe frequencies contained in the pulse. By comparing the results of full dimensional ab initio calculations for the H$^+_2$ molecule with those of a simple sequential model, we demonstrate that, by tuning the chirp parameter, two-photon energy-differential ionization probabilities directly map the wave packet dynamics generated in the molecule. As a result, one can also achieve a significant amount of control of the total ionization yields, with a possible enhancement by more than an order of magnitude.
Attosecond correlation dynamics (PDF)
Abstract: ...Photoemission of an electron is commonly treated as a one-particle phenomenon. With attosecond streaking spectroscopy we observe the breakdown of this single active-electron approximation by recording up to six attoseconds retardation of the dislodged photoelectron due to electronic correlations. We recorded the photon-energy-dependent emission timing of electrons, released from the helium ground state by an extreme-ultraviolet photon, either leaving the ion in its ground state or exciting it into a shake-up state. We identify an optical field-driven d.c. Stark shift of charge-asymmetric ionic states formed after the entangled photoemission as a key contribution to the observed correlation time shift. These findings enable a complete wavepacket reconstruction and are universal for all polarized initial and final states. Sub-attosecond agreement with quantum mechanical ab initio modelling allows us to determine the absolute zero of time in the photoelectric effect to a precision better than 1/25th of the atomic unit of time.
Study of radiative heat transfer in Ångström- and nanometre-sized gaps (PDF)
Abstract: ...Radiative heat transfer in Ångström- and nanometre-sized gaps is of great interest because of both its technological importance and open questions regarding the physics of energy transfer in this regime. Here we report studies of radiative heat transfer in few Å to 5nm gap sizes, performed under ultrahigh vacuum conditions between a Au-coated probe featuring embedded nanoscale thermocouples and a heated planar Au substrate that were both subjected to various surface-cleaning procedures. By drawing on the apparent tunnelling barrier height as a signature of cleanliness, we found that upon systematically cleaning via a plasma or locally pushing the tip into the substrate by a few nanometres, the observed radiative conductances decreased from unexpectedly large values to extremely small ones—below the detection limit of our probe—as expected from our computational results. Our results show that it is possible to avoid the confounding effects of surface contamination and systematically study thermal radiation in Ångström- and nanometre-sized gaps.
Plasmon-exciton-polariton lasing (PDF)
Abstract: ...Metallic nanostructures provide a toolkit for the generation of coherent light below the diffraction limit. Plasmonic-based lasing relies on the population inversion of emitters (such as organic fluorophores) along with feedback provided by plasmonic resonances. In this regime, known as weak light–matter coupling, the radiative characteristics of the system can be described by the Purcell effect. Strong light–matter coupling between the molecular excitons and electromagnetic field generated by the plasmonic structures leads to the formation of hybrid quasi-particles known as plasmon-exciton-polaritons (PEPs). Due to the bosonic character of these quasi-particles, exciton-polariton condensation can lead to laser-like emission at much lower threshold powers than in conventional photon lasers. Here, we observe PEP lasing through a dark plasmonic mode in an array of metallic nanoparticles with a low threshold in an optically pumped organic system. Interestingly, the threshold power of the lasing is reduced by increasing the degree of light–matter coupling in spite of the degradation of the quantum efficiency of the active material, highlighting the ultrafast dynamic responsible for the lasing, i.e., stimulated scattering. These results demonstrate a unique room-temperature platform for exploring the physics of exciton-polaritons in an open-cavity architecture and pave the road toward the integration of this on-chip lasing device with the current photonics and active metamaterial planar technologies.
Exploiting vibrational strong coupling to make an optical parametric oscillator out of a Raman laser (PDF)
Abstract: ...When the collective coupling of the rovibrational states in organic molecules and confined electromagnetic modes is sufficiently strong, the system enters into vibrational strong coupling, leading to the formation of hybrid light-matter quasiparticles. In this Letter, we demonstrate theoretically how this hybridization in combination with stimulated Raman scattering can be utilized to widen the capabilities of Raman laser devices.We explore the conditions under which the lasing threshold can be diminished and the system can be transformed into an optical parametric oscillator. Finally, we show how the dramatic reduction of the many final molecular states into two collective excitations can be used to create an all-optical switch with output in the midinfrared.
Suppressing photochemical reactions with quantized light fields (PDF)
Abstract: ...Photoisomerization, that is, a photochemical reaction leading to a change of molecular structure after absorption of a photon, can have detrimental effects such as leading to DNA damage under solar irradiation, or as a limiting factor for the efficiency of solar cells. Here, we show that strong coupling of organic molecules to a confined light mode can be used to strongly suppress photoisomerization, as well as other photochemical reactions, and thus convert molecules that normally show fast photodegradation into photostable forms.We find this to be especially efficient in the case of collective strong coupling, where the distribution of a single excitation over many molecules and the light mode leads to a collective protection effect that almost completely suppresses the photochemical reaction.
When polarons meet polaritons: Exciton-vibration interactions in organic molecules strongly coupled to confined light fields (PDF)
Abstract: ...We present a microscopic semianalytical theory for the description of organic molecules interacting strongly with a cavity mode. Exciton-vibration coupling within the molecule and exciton-cavity interaction are treated on an equal footing by employing a temperature-dependent variational approach. The interplay between strong exciton-vibration coupling and strong exciton-cavity coupling gives rise to a hybrid ground state, which we refer to as the lower polaron polariton. Explicit expressions for the ground-state wave function, the zero-temperature quasiparticle weight of the lower polaron polariton, the photoluminescence line strength, and the mean number of vibrational quanta are obtained in terms of the optimal variational parameters. The dependence of these quantities upon the exciton-cavity coupling strength reveals that strong cavity coupling leads to an enhanced vibrational dressing of the cavity mode, and at the same time a vibrational decoupling of the dark excitons, which in turn results in a lower polaron polariton resembling a single-mode dressed bare lower polariton in the strong-coupling regime. Thermal effects on several observables are briefly discussed.
Uncoupled Dark States Can Inherit Polaritonic Properties (PDF)
Abstract: ...When a collection of quantum emitters interacts with an electromagnetic field, the whole system can enter into the collective strong coupling regime in which hybrid light-matter states, i.e., polaritons can be created. Only a small portion of excitations in the emitters are coupled to the light field, and there are many dark states that, in principle, retain their pure excitonic nature. Here we theoretically demonstrate that these dark states can have a delocalized character, which is inherent to polaritons, despite the fact that they do not have a photonic component. This unexpected behavior only appears when the electromagnetic field displays a discrete spectrum. In this case, when the main loss mechanism in the hybrid system stems from the radiative losses of the light field, dark states are even more efficient than polaritons in transferring excitations across the structure.
Quantum plasmonics: from jellium models to ab initio calculations (PDF)
Abstract: ...Light-matter interaction in plasmonic nanostructures is often treated within the realm of classical optics. However, recent experimental findings show the need to go beyond the classical models to explain and predict the plasmonic response at the nanoscale. A prototypical system is a nanoparticle dimer, extensively studied using both classical and quantum prescriptions. However, only very recently, fully ab initio time-dependent density functional theory (TDDFT) calculations of the optical response of these dimers have been carried out. Here, we review the recent work on the impact of the atomic structure on the optical properties of such systems. We show that TDDFT can be an invaluable tool to simulate the time evolution of plasmonic modes, providing fundamental understanding into the underlying microscopical mechanisms.
Signatures of Vibrational Strong Coupling in Raman Scattering (PDF)
Abstract: ...We analyze theoretically how the emergence of collective strong coupling between vibrational excitations and confined cavity modes affects Raman scattering processes. This work is motivated by recent experiments [Shalabney et al., Angew. Chemie 54, 7971 (2015)], which reported enhancements of up to three orders of magnitude in the Raman signal. By using different models within linear response theory, we show that the total Raman cross section is maintained constant when the system evolves from the weak-coupling limit to the strong-coupling regime. A redistribution of the Raman signal among the two polaritons is the main fingerprint of vibrational strong coupling in the Raman spectrum.
Radiative heat transfer in the extreme near field (PDF)
Abstract: ...Radiative transfer of energy at the nanometre length scale is of great importance to a variety of technologies including heat-assisted magnetic recording, near-field thermophotovoltaics and lithography. Although experimental advances have enabled elucidation of near-field radiative heat transfer in gaps as small as 20-30 nanometres, quantitative analysis in the extreme near field (less than 10 nanometres) has been greatly limited by experimental challenges. Moreover, the results of pioneering measurements differed from theoretical predictions by orders of magnitude. Here we use custom-fabricated scanning probes with embedded thermocouples, in conjunction with new microdevices capable of periodic temperature modulation, to measure radiative heat transfer down to gaps as small as two nanometres. For our experiments we deposited suitably chosen metal or dielectric layers on the scanning probes and microdevices, enabling direct study of extreme near-field radiation between silica-silica, silicon nitride-silicon nitride and gold-gold surfaces to reveal marked, gap-size-dependent enhancements of radiative heat transfer. Furthermore, our state-of-the-art calculations of radiative heat transfer, performed within the theoretical framework of fluctuational electrodynamics, are in excellent agreement with our experimental results, providing unambiguous evidence that confirms the validity of this theory for modelling radiative heat transfer in gaps as small as a few nanometres. This work lays the foundations required for the rational design of novel technologies that leverage nanoscale radiative heat transfer.
Cavity-Induced Modifications of Molecular Structure in the Strong-Coupling Regime (PDF)
Abstract: ...In most theoretical descriptions of collective strong coupling of organic molecules to a cavity mode, the molecules are modeled as simple two-level systems. This picture fails to describe the rich structure provided by their internal rovibrational (nuclear) degrees of freedom. We investigate a first-principles model that fully takes into account both electronic and nuclear degrees of freedom, allowing an exploration of the phenomenon of strong coupling from an entirely new perspective. First, we demonstrate the limitations of applicability of the Born-Oppenheimer approximation in strongly coupled molecule-cavity structures. For the case of two molecules, we also show how dark states, which within the two-level picture are effectively decoupled from the cavity, are indeed affected by the formation of collective strong coupling. Finally, we discuss ground-state modifications in the ultrastrong-coupling regime and show that some molecular observables are affected by the collective coupling strength, while others depend only on the single-molecule coupling constant.
Harvesting excitons through plasmonic strong coupling (PDF)
Abstract: ...Exciton harvesting is demonstrated in an ensemble of quantum emitters coupled to localized surface plasmons. When the interaction between emitters and the dipole mode of a metallic nanosphere reaches the strong-coupling regime, the exciton conductance is greatly increased. The spatial map of the conductance matches the plasmon field intensity profile, which indicates that transport properties can be tuned by adequately tailoring the field of the plasmonic resonance. Under strong coupling, we find that pure dephasing can have detrimental or beneficial effects on the conductance, depending on the effective number of participating emitters. Finally, we show that the exciton transport in the strong-coupling regime occurs on an ultrafast time scale given by the inverse Rabi splitting (∼10 fs), which is orders of magnitude faster than transport through direct hopping between the emitters.
Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode (PDF)
Abstract: ...We develop a quantum mechanical formalism to treat the strong coupling between an electromagnetic mode and a vibrational excitation of an ensemble of organic molecules. By employing a Bloch-Redfield-Wangsness approach, we show that the influence of dephasing-type interactions, i.e., elastic collisions with a background bath of phonons, critically depends on the nature of the bath modes. In particular, for long-range phonons corresponding to a common bath, the dynamics of the “bright state” (the collective superposition of molecular vibrations coupling to the cavity mode) is effectively decoupled from other system eigenstates. For the case of independent baths (or short-range phonons), incoherent energy transfer occurs between the bright state and the uncoupled dark states. However, these processes are suppressed when the Rabi splitting is larger than the frequency range of the bath modes, as achieved in a recent experiment [Shalabney et al., Nat. Commun. 6, 5981 (2015)]. In both cases, the dynamics can thus be described through a single collective oscillator coupled to a photonic mode, making this system an ideal candidate to explore cavity optomechanics at room temperature.
Extraordinary Exciton Conductance Induced by Strong Coupling (PDF)
Abstract: ...We demonstrate that exciton conductance in organic materials can be enhanced by several orders of magnitude when the molecules are strongly coupled to an electromagnetic mode. Using a 1D model system, we show how the formation of a collective polaritonic mode allows excitons to bypass the disordered array of molecules and jump directly from one end of the structure to the other. This finding could have important implications in the fields of exciton transistors, heat transport, photosynthesis, and biological systems in which exciton transport plays a key role.
Enhancement of near-field radiative heat transfer using polar dielectric thin films (PDF)
Abstract: ...Thermal radiative emission from a hot surface to a cold surface plays an important role in many applications, including energy conversion, thermal management, lithography, data storage and thermal microscopy. Recent studies on bulk materials have confirmed long-standing theoretical predictions indicating that when the gap between the surfaces is reduced to tens of nanometres, well below the peak wavelength of the blackbody emission spectrum, the radiative heat flux increases by orders of magnitude. However, despite recent attempts, whether such enhancements can be obtained in nanoscale dielectric films thinner than the penetration depth of thermal radiation, as suggested by theory, remains experimentally unknown. Here, using an experimental platform that comprises a heat-flow calorimeter with a resolution of about 100 pW, we experimentally demonstrate a dramatic increase in near-field radiative heat transfer, comparable to that obtained between bulk materials, even for very thin dielectric films (50–100 nm) when the spatial separation between the hot and cold surfaces is comparable to the film thickness. We explain these results by analysing the spectral characteristics and mode shapes of surface phonon polaritons, which dominate near-field radiative heat transport in polar dielectric thin films.
Ionization of helium by slow antiproton impact: Total and differential cross sections (PDF)
Abstract: ...We investigate theoretically the single and double ionization of the He atom by antiproton impact for projectile energies ranging from 3 keV up to 1000 keV. We obtain accurate total cross sections by directly solving the fully correlated two-electron time-dependent Schrödinger equation. The cross sections are in excellent agreement with the available experimental data. We also present fully ab initio doubly differential data for single ionization at 10 and 100 keV impact energies and compare to classical-trajectory Monte Carlo calculations. In these differential cross sections we identify the binary-encounter peak along with the anticusp minimum. Furthermore, we also point out the importance of the postcollisional electron-projectile interaction at low antiproton energies, which significantly suppresses electron emission in the forward direction.
Theory of strong coupling between quantum emitters and localized surface plasmons (PDF)
Abstract: ...We theoretically study the emergence of strong coupling in the interaction between quantum emitters and the localized surface plasmons of a metal nanoparticle. Owing to their quasi- degenerate nature, the continuum of multi-poles is shown to behave as a pseudomode strongly coupled to single emitters instead of as a Markovian bath. We demonstrate that the corresponding capping of the induced loss rate enables collective strong coupling to the dipole mode. Numerical simulations and analytical modeling are applied to several configurations of increasing complexity to grasp the relevant physics. In particular, the emitters closest to the nanoparticle surface are proven to contribute the most to the build-up of the plasmon-exciton polaritons, in contrast with the weak-coupling picture of quenching.
Ab initio nanoplasmonics: The impact of atomic structure (PDF)
Abstract: ...We present an ab initio study of the hybridization of localized surface plasmons in a metal nanoparticle dimer. The atomic structure, which is often neglected in theoretical studies of quantum nanoplasmonics, has a strong impact on the optical absorption properties when subnanometric gaps between the nanoparticles are considered. We demonstrate that this influences the hybridization of optical resonances of the dimer, and leads to significantly smaller electric field enhancements as compared to the standard jellium model. In addition, we show that the corrugation of the metal surface at a microscopic scale becomes as important as other well-known quantum corrections to the plasmonic response, implying that the atomic structure has to be taken into account to obtain quantitative predictions for realistic nanoplasmonic devices.
Quantum Emitters Near a Metal Nanoparticle: Strong Coupling and Quenching (PDF)
Abstract: ...We investigate the interplay between quenching and strong coupling in systems that include a collection of quantum emitters interacting with a metal nanoparticle. By using detailed numerical simulations and analytical modeling, we demonstrate that quantum emitters can exhibit strong coupling with the particle dipole resonance at distances at which the quenching to nonradiative channels is expected to dominate the dynamics. These results can be accounted for in terms of the pseudomode character of the higher multipole modes of the nanoparticle and the corresponding reduction of the induced loss rate. These findings expand the current understanding of light-matter interaction in plasmonic systems and could contribute to the development of novel quantum plasmonic platforms.
Entanglement Detection in Coupled Particle Plasmons (PDF)
Abstract: ...When in close contact, plasmonic resonances interact and become strongly correlated. In this work we develop a quantum mechanical model, using the language of continuous variables and quantum information, for an array of coupled particle plasmons. This model predicts that when the coupling strength between plasmons approaches or surpasses the local dissipation, a sizable amount of entanglement is stored in the collective modes of the array. We also prove that entanglement manifests itself in far-field images of the plasmonic modes, through the statistics of the quadratures of the field, in what constitutes a novel family of entanglement witnesses. This protocol is so robust that it is indeed independent of whether our own model is correct. Finally, we estimate the amount of entanglement, the coupling strength and the correlation properties for a system that consists of two or more coupled nanospheres of silver, showing evidence that our predictions could be tested using present-day state-of-the-art technology.
Reflection resonances in surface-disordered waveguides: strong higher-order effects of the disorder (PDF)
Abstract: ...We study coherent wave scattering through waveguides with a step-like surface disorder and find distinct enhancements in the reflection coefficients at well-defined resonance values. Based on detailed numerical and analytical calculations, we can unambiguously identify the origin of these reflection resonances to be higher-order correlations in the surface disorder profile which are typically neglected in similar studies of the same system. A remarkable feature of this new effect is that it relies on the longitudinal correlations in the step profile, although individual step heights are random and thus completely uncorrelated. The corresponding resonances are very pronounced and robust with respect to ensemble averaging, and lead to an enhancement of wave reflection by more than one order of magnitude.
Time delays for attosecond streaking in photoionization of neon (PDF)
Abstract: ...We revisit the time-resolved photoemission in neon atoms as probed by attosecond streaking. We calculate streaking time shifts for the emission of 2p and 2s electrons and compare the relative delay as measured in a recent experiment by Schultze et al. [Science 328, 1658 (2010)]. The B-spline R-matrix method is employed to calculate accurate Eisenbud-Wigner-Smith time delays from multi- electron dipole transition matrix elements for photoionization. The additional laser field-induced time shifts in the exit channel are obtained from separate, time-dependent simulations of a full streaking process by solving the time-dependent Schrödinger equation on the single-active-electron level. The resulting accurate total relative streaking time shifts between 2s and 2p emission lie well below the experimental data. We identify the presence of unresolved shake-up satellites in the experiment as a potential source of error in the determination of streaking time shifts.
What will it take to observe processes in 'real time'? (PDF)
Thermalization and Cooling of Plasmon-Exciton Polaritons: Towards Quantum Condensation (PDF)
Abstract: ...We present indications of thermalization and cooling of quasi-particles, a precursor for quantum condensation, in a plasmonic nanoparticle array. We investigate a periodic array of metallic nanorods covered by a polymer layer doped with an organic dye at room temperature. Surface lattice resonances of the array—hybridized plasmonic/photonic modes—couple strongly to excitons in the dye, and bosonic quasi-particles which we call plasmon-exciton-polaritons (PEPs) are formed. By increasing the PEP density through optical pumping, we observe thermalization and cooling of the strongly coupled PEP band in the light emission dispersion diagram. For increased pumping, we observe saturation of the strong coupling and emission in a new weakly coupled band, which again shows signatures of thermalization and cooling.
Towards hybrid quantum systems: Trapping a single atom near a nanoscale solid-state structure (PDF)
Abstract: ...We describe and demonstrate a method to deterministically trap single atoms near nanoscale solid-state objects. The trap is formed by the interference of an optical tweezer and its reflection from the nano object, creating a one-dimensional optical lattice where the first lattice site is at z0 ~ λ/4 from the surface. Using a tapered optical fiber as the nanoscopic object, we characterize the loading into different lattice sites by means of the AC-Stark shift induced by a guided fiber mode. We demonstrate a loading efficiency of 94(6)% into the first lattice site, and measure the cooperativity for the emission of the atom into the guided mode of the nanofiber. We show that by tailoring the dimensions of the nanofiber the distance of the trap to the surface can be adjusted. This method is applicable to a large variety of nanostructures and represents a promising starting point for interfacing single atoms with arbitrary nanoscale solid-state systems.
Photoionization of helium by attosecond pulses: Extraction of spectra from correlated wave functions (PDF)
Abstract: ...We investigate the photoionization spectrum of helium by attosecond XUV pulses both in the spectral region of doubly excited resonances as well as above the double ionization threshold. In order to probe for convergence, we compare three techniques to extract photoelectron spectra from thewave packet resulting from the integration of the time-dependent Schrödinger equation in a finite-element discrete variable representation basis. These techniques are projection on products of hydrogenic bound and continuum states, projection onto multichannel scattering states computed in a B-spline close-coupling basis, and a technique based on exterior complex scaling implemented in the same basis used for the time propagation. Thesemethods allowone to monitor the population of continuum states in wave packets created with ultrashort pulses in different regimes. Applications include photo cross sections and anisotropy parameters in the spectral region of doubly excited resonances, time-resolved photoexcitation of autoionizing resonances in an attosecond pump-probe setting, and the energy and angular distribution of correlated wave packets for two-photon double ionization.
Coupling a Single Trapped Atom to a Nanoscale Optical Cavity (PDF)
Abstract: ...Hybrid quantum devices, where dissimilar quantum systems are combined to attain qualities not available with either system alone, may enable far-reaching control in quantum measurement, sensing, and information processing. A paradigmatic example is trapped ultra-cold atoms, which offer excellent quantum coherent properties, coupled to nanoscale solid-state systems, which allow for strong interactions. We demonstrate a deterministic interface between a single trapped rubidium atom and a nanoscale photonic crystal cavity. Precise control over the atom's position allows us to probe the cavity near-field with a resolution below the diffraction limit, and to observe large atom-photon coupling. This approach may enable the realization of integrated, strongly coupled quantum nano-optical circuits.
Nanoplasmonic near-field synthesis (PDF)
Abstract: ...The temporal response of resonances in nanoplasmonic structures typically converts an incoming few-cycle field into a much longer near-field at the spot where non-linear physical phenomena including electron emission, recollision and high-harmonic generation can take place. We show that for practically useful structures pulse shaping of the incoming pulse can be used to synthesize the plasmon-enhanced field and enable single-cycle driven nonlinear physical phenomena. Our method is demonstrated for the generation of an isolated attosecond pulse by plasmon-enhanced high harmonic generation. We furthermore show that optimal control techniques can be used even if the response of the plasmonic structure is not known a priori.
Autoionization of Molecular Hydrogen: Where do the Fano Lineshapes Go? (PDF)
Abstract: ...Atomic autoionization following photoabsorption is a typical example of quantum interferences governed by electron-electron correlation. Coherence between direct photoionization and autoionization paths results in "Fano profiles", widely explored in atoms in the last 60 years. The advent of femto- and attosecond laser technology made time-resolved images of the delayed electron ejection in autoionization accessible, leading to the reemergence of such studies in atomic systems. The counterpart molecular phenomena show the richness, as well as the complexity, added by nuclear motion, which may proceed on similar time scales. However, Fano profiles are usually absent in measured molecular photoionization cross sections and an unequivocal parametrization of molecular autoionization signatures, similar to that introduced by Fano in atoms [U. Fano, Phys. Rev. 1961, 124, 1866] has not yet been achieved. In this work we introduce a simple semiclassical model that accounts for all the features observed in H2 photoionization and demonstrate that the interference structures observed in dissociative ionization spectra are almost exclusively due to the phase accumulated in the nuclear motion. Furthermore, we show that the temporal build-up of these structures in the energy-differential cross sections is also determined by nuclear motion. We validate our models by comparing with full-dimensional ab initio calculations solving the time-dependent Schrödinger equation.
Nanoplasmonic Lattices for Ultracold Atoms (PDF)
Abstract: ...We propose to use sub-wavelength confinement of light associated with the near field of plasmonic systems to create nanoscale optical lattices for ultracold atoms. Our approach combines the unique coherence properties of isolated atoms with the sub-wavelength manipulation and strong light-matter interaction associated with nano-plasmonic systems. It allows one to considerably increase the energy scales in the realization of Hubbard models and to engineer effective long-range interactions in coherent and dissipative many-body dynamics. Realistic imperfections and potential applications are discussed.
Probing scattering phase shifts by attosecond streaking (PDF)
Abstract: ...Attosecond streaking is one of the most fundamental processes in attosecond science allowing for a mapping of temporal (i.e. phase) information on the energy domain. We show that on the single-particle level attosecond streaking time shifts contain spectral phase information associated with the Eisenbud-Wigner-Smith (EWS) time delay, provided the influence of the streaking infrared field is properly accounted for. While the streaking phase shifts for short-ranged potentials agree with the associated EWS delays, Coulomb potentials require special care. We show that the interaction between the outgoing electron and the combined Coulomb and IR laser fields lead to a streaking phase shift that can be described classically.
Multielectron Transitions Induced by Neutron Impact on Helium (PDF)
Abstract: ...We explore excitation and ionization by neutron impact as a novel tool for the investigation of electron-electron correlations in helium. We present single- and double-ionization spectra calculated in accurate numerical ab initio simulations for incoming neutrons with kinetic energies of up to 150 keV. The resulting electron spectra are found to be fundamentally different from photoionization or charged particle impact due to the intrinsic many-body character of the interaction. In particular, doubly excited resonances that are strongly suppressed in electron or photon impact become prominent. The ratio of double to single ionization is found to differ significantly from those of photon and charged-particle impact.
Attosecond Pump-Probe of Doubly Excited States of Helium through Two-Photon Interferometry
Abstract: ...We show that correlated dynamics in wave packets of doubly excited helium can be followed in real time by a pump-probe setup based on two-photon interferometry. This approach promises to map the evolution of the two-electron wave packet onto experimentally easily accessible non-coincident single electron spectra.
Attosecond Streaking of Correlated Two-Electron Transitions in Helium (PDF)
Abstract: ...We present fully ab initio simulations of attosecond streaking for ionization of helium accompanied by shakeup of the second electron. This process represents a prototypical case for strongly correlated electron dynamics on the attosecond time scale. We show that streaking spectroscopy can provide detailed information on the Eisenbud-Wigner-Smith time delay as well as on the infrared-field dressing of both bound and continuum states. We find a novel contribution to the streaking delay that stems from the interplay of electron-electron and infrared-field interactions in the exit channel. We quantify all the contributions with attosecond precision and provide a benchmark for future experiments.
Time shifts in photoemission from a fully correlated two-electron model system (PDF)
Abstract: ...We theoretically investigate time-resolved photoemission originating from two different shells (1s and 2p) of a fully correlated atomic two-electron model system ionized by an extreme-ultraviolet attosecond light pulse. The parameters of the model system are tuned such that the ionization potentials of the 1s and 2p electrons have values close to those of the 2s and 2p levels in a neon atom, for which a relative time delay has been measured in a recent attosecond streaking experiment by Schultze et al. [Science 328, 1658 (2010)]. Up to now theoretical efforts could account only for delays more than a factor of 2 shorter than the reported experimental value. By solving the time-dependent Schrödinger equation numerically exactly we explore the influence of correlations on the time delay previously implicated as one of the potential sources of discrepancies. We investigate the influence of the interplay between electron interactions and the probing streaking infrared field on the extracted relative delays between the two emission channels. We find that for our model system the inclusion of electronic correlation only slightly modifies the time shifts, as compared to a mean-field treatment. In particular, the correlation-induced time delay is contained in the Eisenbud-Wigner-Smith time delay for the photoionization process.
Attosecond Two-Photon Interferometry for Doubly Excited States of Helium (PDF)
Abstract: ...We show that the correlation dynamics in coherently excited doubly excited resonances of helium can be followed in real time by two-photon interferometry. This approach promises to map the evolution of the two-electron wave packet onto experimentally easily accessible noncoincident single-electron spectra. We analyze the interferometric signal in terms of a semianalytical model which is validated by a numerical solution of the time-dependent two-electron Schrödinger equation in its full dimensionality.
Recent Advances in Computational Methods for the Solution of the Time-Dependent Schrödinger Equation for the Interaction of Short, Intense Radiation with One and Two-Electron Systems: Application to He and H2+
Abstract: ...In the past few years new and efficient algorithms have been developed to solve the time-dependent Schrödinger equation (TDSE) for few-electron systems. When coupled with the advances in and availability of high performance computing platforms, it is now possible to numerically calculate nearly exact solutions to the interactions of short, intense laser pulses with simple one and two-electron systems. In addition, somewhat less accurate treatments of the heavier rare gases and simple two-electron molecules are also becoming available. The proceedings from this workshop have provided a unique opportunity to describe the substantial numerical and algorithmic progress that has been achieved over the past few years to solve the TDSE and to illustrate them on the He atom and H2+ molecule.
Universal features in sequential and nonsequential two-photon double ionization of helium (PDF)
Abstract: ...We analyze two-photon double ionization of helium in both the nonsequential (ℏω < I2 ≈ 54.4 eV) and sequential (ℏω > I2) regime. We show that the energy spacing ΔE=E1-E2 between the two emitted electrons provides the key parameter that controls both the energy and the angular distribution and reveals the universal features present in both the nonsequential and sequential regime. This universality, i.e., independence of ℏω, is a manifestation of the continuity across the threshold for sequential double ionization. For all photon energies considered, the energy distribution can be described by a universal shape function that contains only the spectral and temporal information entering second-order time-dependent perturbation theory. Angular correlations and distributions are found to be more sensitive to the value of ℏω. In particular, shake-up interferences have a large effect on the angular distribution. Energy spectra, angular distributions parametrized by the anisotropy parameters βj, and total cross sections presented in this paper are obtained by fully correlated time-dependent ab initio calculations.
Time-resolved photoemission by attosecond streaking: extraction of time information (PDF)
Abstract: ...Attosecond streaking of atomic photoemission holds the promise to provide unprecedented information on the release time of the photoelectron. We show that attosecond streaking phase shifts indeed contain timing (or spectral phase) information associated with the Eisenbud–Wigner–Smith time delay matrix of quantum scattering. However, this is only accessible if the influence of the streaking infrared (IR) field on the emission process is properly accounted for. The IR probe field can strongly modify the observed streaking phase shift. We show that the part of the phase shift ('time shift') due to the interaction between the outgoing electron and the combined Coulomb and IR laser fields can be described classically. By contrast, the strong initial-state dependence of the streaking phase shift is only revealed through the solution of the time-dependent Schrödinger equation in its full dimensionality. We find a time delay between the hydrogenic 2s and 2p initial states in He+ exceeding 20 as for a wide range of IR intensities and XUV energies.
Differential cross sections for non-sequential double ionization of He by 52 eV photons from the Free Electron Laser in Hamburg, FLASH (PDF)
Abstract: ...Two-photon double ionization of He is studied at the Free Electron Laser in Hamburg (FLASH) by inspecting He2+ momentum distributions at 52 eV photon energy. We demonstrate that recoil ion momentum distributions can be used to infer information about highly correlated electron dynamics and find the first experimental evidence for 'virtual sequential ionization'. The experimental data are compared with the results of two calculations, both solving the time-dependent Schrödinger equation. We find good overall agreement between experiment and theory, with significant differences for cuts along the polarization direction that cannot be explained by the experimental resolution alone.
Delay in Photoemission (PDF)
Abstract: ...Photoemission from atoms is assumed to occur instantly in response to incident radiation and provides the basis for setting the zero of time in clocking atomic-scale electron motion. We used attosecond metrology to reveal a delay of 21 ± 5 attoseconds in the emission of electrons liberated from the 2p orbitals of neon atoms with respect to those released from the 2s orbital by the same 100-electron volt light pulse. Small differences in the timing of photoemission from different quantum states provide a probe for modeling many-electron dynamics. Theoretical models refined with the help of attosecond timing metrology may provide insight into electron correlations and allow the setting of the zero of time in atomic-scale chronoscopy with a precision of a few attoseconds.
Nanowires with surface disorder: Giant localization length and dynamical tunneling in the presence of directed chaos (PDF)
Abstract: ...We investigate electronic quantum transport through nanowires with one-sided surface roughness in the presence of a perpendicular magnetic field. Exponentially diverging localization lengths are found in the quantum-to-classical crossover regime, controlled by tunneling between regular and chaotic regions of the underlying mixed classical phase space. We show that each regular mode possesses a well-defined mode-specific localization length. We present analytic estimates of these mode localization lengths which agree well with the numerical data. The coupling between regular and chaotic regions can be determined by varying the length of the wire leading to intricate structures in the transmission probabilities. We explain these structures quantitatively by dynamical tunneling in the presence of directed chaos.
Ab initio calculations of two-electron emission by attosecond pulses (PDF)
Abstract: ...Recent experimental developments of high-intensity, short-pulse XUV light sources are enhancing our ability to study electron-electron correlations. We perform time-dependent calculations to investigate the so-called "sequential" regime (ℏω > 54.4 eV) in the two-photon double ionization of helium. We show that attosecond pulses allow to not only probe but also to induce angular and energy correlations of the emitted electrons. Electron correlation induced by the time correlation between emission events manifests itself in the angular distribution of the ejected electrons. The final momentum distribution reveals regions dominated by the Wannier ridge break-up scenario and by post-collision interaction. In addition, we find evidence for an interference between direct ("nonsequential") and indirect ("sequential") double photo-ionization with intermediate shake-up states, the strength of which is controlled by the pulse duration.
Probing Electron Correlation via Attosecond xuv Pulses in the Two-Photon Double Ionization of Helium (PDF)
Abstract: ...Recent experimental developments of high-intensity, short-pulse extreme ultraviolet light sources are enhancing our ability to study electron-electron correlations. We perform time-dependent calculations to investigate the so-called “sequential” regime (ℏω>54.4 eV) in the two-photon double ionization of helium. We show that attosecond pulses allow us not only to probe but also to induce angular and energy correlations of the emitted electrons. The final momentum distribution reveals regions dominated by the Wannier ridge breakup scenario and by postcollision interaction.
Electron correlation in two-photon double ionization of helium from attosecond to XFEL pulses (PDF)
Abstract: ...We investigate the role of electron correlation in the two-photon double ionization of helium for ultrashort pulses in the extreme ultraviolet (XUV) regime with durations ranging from a hundred attoseconds to a few femtoseconds. We perform time-dependent ab initio calculations for pulses with mean frequencies in the so-called 'sequential' regime (ℏω > 54.4 eV). Electron correlation induced by the time correlation between emission events manifests itself in the angular distribution of the ejected electrons, which strongly depends on the energy sharing between them. We show that for ultrashort pulses two-photon double ionization probabilities scale non-uniformly with pulse duration depending on the energy sharing between the electrons. Most interestingly we find evidence for an interference between direct ('nonsequential') and indirect ('sequential') double photoionization with intermediate shake-up states, the strength of which is controlled by the pulse duration. This observation may provide a route towards measuring the pulse duration of x-ray free-electron laser (XFEL) pulses.
Nonsequential two-photon double ionization of helium (PDF)
Abstract: ...We present accurate time-dependent ab initio calculations on fully differential and total integrated (generalized) cross sections for the non-sequential two-photon double ionization of helium at photon energies from 40 eV to 54 eV. Our computational method is based on the solution of the time-dependent Schroedinger equation and subsequent projection of the wave function onto Coulomb waves. We compare our results with other recent calculations and discuss the emerging similarities and differences. We investigate the role of electronic correlation in the representation of the two-electron continuum states, which are used to extract the ionization yields from the fully-correlated final wave function. In addition, we study the influence of the pulse length and shape on the cross sections in time-dependent calculations and address convergence issues.
General approach to few-cycle intense laser interactions with complex atoms (PDF)
Abstract: ...A general ab initio and nonperturbative method to solve the time-dependent Schrödinger equation (TDSE) for the interaction of a strong attosecond laser pulse with a general atom, i.e., beyond the models of quasi-one-electron or quasi-two-electron targets, is described. The field-free Hamiltonian and the dipole matrices are generated using a flexible B-spline R-matrix method. This numerical implementation enables us to construct term-dependent, nonorthogonal sets of one-electron orbitals for the bound and continuum electrons. The solution of the TDSE is propagated in time using the Arnoldi-Lanczos method, which does not require the diagonalization of any large matrices. The method is illustrated by an application to the multiphoton excitation and ionization of Ne atoms. Good agreement with R -matrix Floquet calculations for the generalized cross sections for two-photon ionization is achieved.
Nanowires with Surface Disorder: Giant Localization Lengths and Quantum-to-Classical Crossover (PDF)
Abstract: ...We investigate electronic quantum transport through nanowires with one-sided surface roughness. A magnetic field perpendicular to the scattering region is shown to lead to exponentially diverging localization lengths in the quantum-to-classical crossover regime. This effect can be quantitatively accounted for by tunneling between the regular and the chaotic components of the underlying mixed classical phase space.
A Modular Method for the Efficient Calculation of Ballistic Transport Through Quantum Billiards
Abstract: ...We present a numerical method which allows to efficiently calculate quantum transport through phase-coherent scattering structures, so-called "quantum billiards”. Our approach consists of an extension of the commonly used Recursive Green’s Function Method (RGM), which proceeds by a discretization of the scattering geometry on a lattice with nearest-neighbour coupling. We show that the efficiency of the RGM can be enhanced considerably by choosing symmetry-adapted grids reflecting the shape of the billiard. Combining modules with different grid structure to assemble the entire scattering geometry allows to treat the quantum scattering problem of a large class of systems very efficiently. We will illustrate the computational challenges involved in the calculations and present results that have been obtained with our method.
Two-photon double ionization of helium (PDF)
Transport through quantum wires with surface disorder (PDF)