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Strong coupling between molecules and quantized fields has emerged as an effective methodology to engineer molecular properties. New hybrid states are formed when molecules interact with quantized fields. Since the properties of these states can be modulated by fine-tuning the field features, an exciting and new side of chemistry can be explored. In particular, significant modifications of the molecular properties can be achieved in plasmonic nanocavities, where the field quantization volume is reduced to sub-nanometric volumes. Intriguing applications of nanoplasmonics include the possibility of coupling the plasmons with a single molecule, instrumental for sensing, high-resolution spectroscopy, and single-molecule imaging. In this work, we focus on phenomena where the simultaneous effects of multiple plasmonic modes are critical. We propose a theoretical methodology to account for many plasmonic modes simultaneously while retaining computational feasibility. Our approach is conceptually simple and allows us to accurately account for the multimode effects and rationalize the nature of the interaction between multiple plasmonic excitations and molecules., 27 pages, 6 figures

Geometries to reproduce the calculations in the supporting information of "Riso, R. R., Haugland, T. S., Ronca, E., & Koch, H. (2022). On the characteristic features of ionization in QED environments.arXiv preprint arXiv:2203.06050." The field is oriented on the z direction

Plasmonic nanocavities enable the confinement of molecules and electromagnetic fields within nano-metric volumes. As a consequence, the molecules experience a remarkably strong interaction with the electromagnetic field, to such an extent that the quantum states of the system become hybrids between light and matter: polaritons. Here we present a non-perturbative method to simulate the emerging properties of such polaritons: it combines a high-level quantum chemical description of the molecule with a quantized description of the localized surface plasmons in the nanocavity. We apply the method to molecules of realistic complexity in a typical plasmonic nanocavity, featuring also a subnanometric asperity (picocavity). Our results disclose the effects of the mutual polarization and correlation of plasmons and molecular excitations, disregarded so far. They also quantify to what extent the molecular charge density can be manipulated by nanocavities, and stand as benchmarks to guide the development of methods for molecular polaritonics., Comment: 13 Pages Main text, 4 Figures and 11 pages Supporting Information

The e

The eT program is an open source electronic structure package with emphasis on coupled cluster and multilevel methods. It includes efficient spin adapted implementations of ground and excited singlet states, as well as equation of motion oscillator strengths, for CCS, CC2, CCSD, and CC3. Furthermore, eT provides unique capabilities such as multilevel Hartree-Fock and multilevel CC2, real-time propagation for CCS and CCSD, and efficient CC3 oscillator strengths. With a coupled cluster code based on an efficient Cholesky decomposition algorithm for the electronic repulsion integrals, eT has similar advantages as codes using density fitting, but with strict error control. Here we present the main features of the program and demonstrate its performance through example calculations. Because of its availability, performance, and unique capabilities, we expect eT to become a valuable resource to the electronic structure community., 31 pages and 10 figures - supplementary information included in the uploaded files

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 nonperturbative 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., We acknowledge computing resources through UNINETT Sigma2 (National Infrastructure for High Performance Computing and Data Storage in Norway) through Project No. NN2962k. We acknowledge funding from the Marie Skłodowska-Curie European Training Network COSINE (Computational Spectroscopy in Natural Sciences and Engineering) Grant Agreement No. 765739, and the Research Council of Norway through FRINATEK Projects No. 263110 and No. 275506. A. R. was supported by the European Research Council (ERC-2015-AdG694097), the Cluster of Excellence Advanced Imaging of Matter (AIM), and Grupos Consolidados Grants No. IT1249-19 and No. SFB925. The Flatiron Institute is a division of the Simons Foundation.