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 ultra-strong coupling regime and show that some molecular observables are affected by the collective coupling strength, while others only depend on the single-molecule coupling constant.
Cavity polaritonics is capturing the imagination of the chemistry community because of the novel opportunities it creates to direct chemistry. Electron transfer (ET) reactions are among the simplest reactions, and they also underpin bioenergetics. As such, new conceptual strategies to manipulate and direct electron flow at the nanoscale are of wide-ranging interest in biochemistry, energy science, bio-inspired materials science, and chemistry. We show that optical cavities can modulate electron transfer pathway interferences and ET rates in donor-bridge-acceptor (DBA) systems. We derive the ra…
This work provides the fundamental theoretical framework for the molecular cavity Quantum Electrodynamics by resolving the gauge ambiguities between the Coulomb gauge and the dipole gauge Hamiltonian under the electronic state truncation. Our conjecture for the arising of such gauge ambiguity is that not all operators are properly constrained in the truncated electronic subspace. Based upon this conjecture, we construct a unitary transformation that properly constrains all operators in the subspace, and derive an equivalent and yet convenient expression for the Coulomb gauge Hamiltonian under …
Recent experiments have suggested that ground state chemical kinetics can be suppressed or enhanced by coupling the vibrational degrees of freedom of a molecular system with a radiation mode inside an optical cavity. Experiments show that the chemical rate is strongly modified when the photon frequency is close to characteristic vibrational frequencies. The origin of this remarkable effect remains unknown. In this work, we develop an analytical rate theory for cavity-modified ground state chemical kinetics based on the Pollak-Grabert-Hänggi rate theory. Unlike previous work, our theory covers …
We present an ab initio correlated approach to study molecules that interact strongly with quantum fields in an optical cavity. Quantum electrodynamics coupled cluster theory provides a non-perturbative description of cavity-induced effects in ground and excited states. Using this theory, we show how quantum fields can be used to manipulate charge transfer and photochemical properties of molecules. We propose a strategy to lift electronic degeneracies and induce modifications in the ground state potential energy surface close to a conical intersection.
Cavity-mediated localization and collective electron correlation phases
Zurich University of Applied Sciences（苏黎世应用科技大学）；Max Planck Institute for the Structure and Dynamics of Matter（马克斯·普朗克物质结构动力学研究所）；Center for Free-Electron Laser Science（自由电子激光科学中心）；The Hamburg Center for Ultrafast Imaging（汉堡超快成像中心）；Center for Computational Quantum Physics (CCQ)（计算量子物理中心）；Initiative for Computational Catalysis (ICC)（计算催化倡议）；The Flatiron Institute（平顿研究所）
We show that the correspondence between quantum and classical mechanics can be tuned by varying the coupling strength between the cavity modes and an atom or a molecule. In the acceleration gauge the cavity-matter system is represented by an effective Hamiltonian with a non-trivial coupling appearing in the potential, and a renormaized mass. Importantly, the acceleration-gauge coupling is non-monotonic with the strength cavity-matter interaction. As a result one obtain effective approximately decoupled field-matter dynamics for weak and strong interactions. In the weak coupling regime the effe…
We introduce 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 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 ($\simμ$m). We show that this can lead to effective long-range heat transport between molecu…
Nonadiabatic phenomena are investigated in the rovibrational motion of molecules confined in an infrared cavity. Conical intersections (CIs) between vibrational polaritons, similar to CIs between electronic polaritonic surfaces, are found. The spectral, topological, and dynamic properties of the vibrational polaritons show clear fingerprints of nonadiabatic couplings between molecular vibration, rotation and the cavity photonic mode. Furthermore, it is found that for the investigated system, composed of two rovibrating HCl molecules and the cavity mode, breaking the molecular permutational sym…
We propose a mechanism to realize high-yield molecular formation from ultracold atoms. Atom pairs are continuously excited by a laser, and a collective decay into the molecular ground state is induced by a coupling to a lossy cavity mode. Using a combination of analytical and numerical techniques, we demonstrate that the molecular yield can be improved by simply increasing the number of atoms, and can overcome efficiencies of state-of-the-art association schemes. We discuss realistic experimental setups for diatomic polar and nonpolar molecules, opening up collective light matter interactions …
Cooling a range of molecules to ultracold temperatures (<1 mK) is a difficult but important challenge in molecular physics and chemistry. Collective cavity cooling of molecules is a promising method that does not rely on molecular energy level and thus can be applied to all molecules in principle. However, the initial lack of cold molecules leads to the difficulty in its experimental implementation. We show that efficient collective sympathetic cooling of molecules to sub-mK temperatures using a large ensemble of atoms within a cavity is feasible. This approach is a new type of sympathetic coo…
Despite the potential paradigm breaking capability of microcavities to control chemical processes, the extent to which photonic devices change properties of molecular materials is still unclear, in part due to challenges in modeling hybrid light-matter excitations delocalized over many length scales. We overcome these challenges for a photonic wire under strong coupling with a molecular ensemble. Our simulations provide a detailed picture of the effect of photonic wires on spectral and transport properties of a disordered molecular material. We find stronger changes to the probed molecular obs…
Evidence for cavity-induced metallic phase from entropic electron correlation effects
Max Planck Institute for the Structure and Dynamics of Matter（马克斯·普朗克物质与结构动力学研究所）；Center for Free-Electron Laser Science（自由电子激光科学中心）；The Hamburg Center for Ultrafast Imaging（汉堡超快成像中心）；Zurich University of Applied Sciences, School of Engineering（苏黎世应用科技大学工程学院）
