On the characteristic features of ionization in QED environments.

The ionization of molecular systems is important in many chemical processes, such as electron transfer and hot electron injection. Strong coupling between molecules and quantized fields (e.g., inside optical cavities) represents a new promising way to modify molecular properties in a non-invasive way. Recently, strong light-matter coupling has shown the potential to significantly improve the rates of hot electron driven processes, for instance, in water splitting. In this paper, we demonstrate that inside an optical cavity, the residual interaction between an outgoing free electron and the vacuum field is significant. We further show that since the quantized field is also interacting with the ionized molecule, the free electron and the molecular system are correlated. We develop a theoretical framework to account for the field induced correlation and show that the interaction between the free electron and the field, free electron-field interaction, has sizable effects on the ionization potential of typical organic molecules.

Strong Coupling to Circularly Polarized Photons: Toward Cavity-Induced Enantioselectivity.

The development of new methodologies for the selective synthesis of individual enantiomers is still one of the major challenges in synthetic chemistry. Many biomolecules, and also many pharmaceutical compounds, are indeed chiral. While the use of chiral reactants or catalysts has led to substantial progress in the field of asymmetric synthesis, a systematic approach applicable to general reactions has still not been proposed. In this work, we demonstrate that strong coupling to circularly polarized fields can induce asymmetry in otherwise nonselective reactions. Specifically, we show that the field induces stereoselectivity in the early stages of chemical reactions by selecting an energetically preferred direction of approach for the reagents. Although the effects observed thus far are too small to significantly drive asymmetric synthesis, our results provide a proof of principle for field-induced stereoselective mechanisms. These findings lay the groundwork for future research.

Toward Polaritonic Molecular Orbitals for Large Molecular Systems.

A comprehensive understanding of electron-photon correlation is essential for describing the reshaping of molecular orbitals in quantum electrodynamics (QED) environments. The strong coupling QED Hartree-Fock (SC-QED-HF) theory tackles these aspects by providing consistent molecular orbitals in the strong coupling regime. The previous implementation, however, has significant convergence issues that limit the applicability. In this work, we introduce two second-order algorithms that significantly reduce the computational requirements, thereby enhancing the modeling of large molecular systems in QED environments. Furthermore, the implementation will enable the development of correlated methods based on a reliable molecular orbital framework as well as multi-level methodologies able to model the inclusion of solvent effects in this kind of complex systems.

Molecular orbital theory in cavity QED environments.

Coupling between molecules and vacuum photon fields inside an optical cavity has proven to be an effective way to engineer molecular properties, in particular reactivity. To ease the rationalization of cavity induced effects we introduce an ab initio method leading to the first fully consistent molecular orbital theory for quantum electrodynamics environments. Our framework is non-perturbative and explains modifications of the electronic structure due to the interaction with the photon field. In this work, we show that the newly developed orbital theory can be used to predict cavity induced modifications of molecular reactivity and pinpoint classes of systems with significant cavity effects. We also investigate electronic cavity-induced modifications of reaction mechanisms in vibrational strong coupling regimes.