A series of experiments demonstrate that strong light-matter coupling between vibrational excitations in isotropic solutions of molecules and resonant infrared optical microcavity modes leads to modified thermally-activated kinetics. However, Feist and coworkers [\emph{Phys. Rev. X.}, \textbf{9}, 021057(2019)] have recently demonstrated that, within transition state theory, the effects of strong light-matter coupling with reactive modes are electrostatic and essentially independent of light-matter resonance or even of the formation of vibrational polaritons. To analyze this puzzling theoretical result in further detail, we revisit it under a new light, invoking a normal mode analysis of the transition state and reactant configurations for an ensemble of an arbitrary number of molecules in a cavity, obtaining simple analytical expressions that produce similar conclusions as Feist. While these effects become relevant in optical microcavities if the molecular dipoles are anisotropically aligned, or in cavities with extreme confinement of the photon modes, they become negligible for isotropic solutions in microcavities. It is concluded that further studies are necessary to track the origin of the experimentally observed kinetics.
The electromagnetic field in an optical cavity can dramatically modify and even control chemical reactivity via vibrational strong coupling (VSC). Since the typical vibration and cavity frequencies are considerably higher than thermal energy, it is essential to adopt a quantum description of cavity-catalyzed adiabatic chemical reactions. Using quantum transition state theory (TST), we examine the coherent nature of adiabatic reactions and derive the cavity-induced changes in eigen frequencies, zero-point-energy, and quantum tunneling. The resulting quantum TST calculation allows us to explain …
We consider an ensemble of diatomic molecules resonantly coupled to an optical cavity under strong coupling conditions at normal incidence. Photodissociation dynamics is examined via direct numerical integration of the coupled Maxwell-Schrodinger equations with molecular ro-vibrational degrees of freedom explicitly taken into account. It is shown that the dissociation is significantly affected (slowed down) when the system is driven at its polaritonic frequencies. The observed effect is demonstrated to be of transient nature and has no classical analog. An intuitive explanation of the dissocia…
Polaritonic chemistry has become a rapidly developing field within the last few years. A multitude of experimental observations suggest that chemical properties can be fundamentally altered and novel physical states appear when matter is strongly coupled to resonant cavity modes, i.e. when hybrid light-matter states emerge. Up until now, theoretical approaches to explain and predict these observations were either limited to phenomenological quantum optical models, suited to describe collective polaritonic effects, or alternatively to ab initio approaches for small system sizes. The later metho…
The interaction of a molecule with the quantized electromagnetic field of a nano-cavity gives rise to light-induced conical intersections between polaritonic potential energy surfaces. We demonstrate for a realistic model of a polyatomic molecule that the time-resolved ultrafast radiative emission of the cavity enables to follow both nuclear wavepacket dynamics on and nonadiabatic population transfer between polaritonic surfaces without applying a probe pulse. The latter provides an unambiguous (and in principle experimentally accessible) dynamical fingerprint of light-induced conical intersec…
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 i…
I investigate the tunneling decay rate of a polaritonic system formed by a strong coupling between a vacuum cavity mode and $N$ metastable systems. Using a simple model potential, I find the instanton solutions controlling the low-temperature tunneling rate. The resulting rate modification due to the cavity is proportional to the mean of the second power of the light-matter coupling. No collective effect that would enhance the rates by a factor of $\sqrt{N}$ is present, which is in line with the results in the thermal activation regime.
Recent experiments and theory demonstrate that the the ground state properties and chemical reactivity of molecules can be modified inside an optical cavity. The vibrational strong or ultrastrong coupling results in the formation of vibrational polaritons which are usually observed through infrared spectra (IR). Here, we provide a theoretical framework to conduct multidimensional quantum simulations of the infrared spectra when the molecule is interacting with cavity modes. Taking single water molecule as an example, combing with accurate potential energy and dipole moment surfaces, our implem…
In the field of polaritonic chemistry, strong light-matter interactions are used to alter a chemical reaction inside an optical cavity. To explain and understand these processes, the development of reliable theoretical models is essential. While traditional methods have to balance accuracy and system size, new developments in quantum computing, in particular the Variational Quantum Eigensolver (VQE), offer a path for an accurate solution of the electronic Schrödinger equation with the promise of polynomial scaling and eventual quasi-exact solutions on currently available quantum devices. In th…
Collectively coupling molecular ensembles to a cavity has been demonstrated to modify chemical reactions akin to catalysis. Theoretically understanding this experimental finding remains to be an important challenge. In particular the role of quantum effects in such setups is an open question of fundamental and practical interest. Theoretical descriptions often neglect quantum entanglement between nuclear and electro-photonic degrees of freedom, e.g.~by computing Ehrenfest dynamics. Here we discover that disorder can strongly enhance the build-up of this entanglement on short timescales after i…
It has been experimentally demonstrated that reaction rates for molecules embedded in microfluidic optical cavities are altered when compared to rates observed under "ordinary" reaction conditions. However, precise mechanisms of how strong coupling of an optical cavity mode to molecular vibrations affect the reactivity and how resonance behavior emerges are still under dispute. In the present work, we approach these mechanistic issues from the perspective of a thermal model reaction, the inversion of ammonia along the umbrella mode, in presence of a single cavity mode of varying frequency and …
We study theoretically the quantum dynamics and spectroscopy of rovibrational polaritons formed in a model system composed of a single rovibrating diatomic molecule, which interacts with two degenerate, orthogonally polarized modes of an optical Fabry-Pérot cavity. We employ an effective rovibrational Pauli-Fierz Hamiltonian in length gauge representation and identify three-state vibro-polaritonic conical intersections (VPCIs) between singly-excited vibro-polaritonic states in a two-dimensional angular coordinate branching space. The lower and upper vibrational polaritons are of mixed light-ma…
We find and analyze the exact time-dependent potential energy surface driving the proton motion for a model of cavity-induced suppression of proton-coupled electron-transfer. We show how, in contrast to the polaritonic surfaces, its features directly correlate to the proton dynamics and discuss cavity-modifications of its structure responsible for the suppression. The results highlight the interplay between non-adiabatic effects from coupling to photons and coupling to electrons, and suggest caution is needed when applying traditional dynamics methods based on polaritonic surfaces.
