Theory of cavity-modified ground-state chemical reactivity
Abstract: ...Here we present a fundamental study on how the ground-state chemical reactivity of a molecule can be modified in a QED scenario, i.e., when it is placed inside a 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 largely modify potential barriers of activation 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. Then we 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. Finally, we discuss resonance effects in this process and the case of many-molecule strong coupling. Here we speculate about the possibility of orientational alignment of the dipoles induced by collective strong coupling as a supplementary mechanism for modifying ground-state chemical reactivity of an ensemble of molecules inside a cavity.
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.
Tensor Network simulation of polaron-polaritons in organic microcavities
Abstract: ...In the regime of strong coupling between molecular excitons and confined optical modes, the intra-molecular 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 characterised by low-frequency (sub-Ohmic) modes.
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.
Exploring the Limits of Super-Planckian Far-Field Radiative Heat Transfer Using 2D Materials
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.
Tensor network simulation of non-Markovian dynamics in organic polaritons
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 analyse 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.
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.