Strong coupling between localized surface plasmons and molecules by coupled cluster theory

Abstract

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.

arXiv comment13 Pages Main text, 4 Figures and 11 pages Supporting Information

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Cited by in corpus (14)

• Theoretical Challenges in Polaritonic Chemistry
• Molecular orbital theory in cavity QED environments
• A theoretical perspective on molecular polaritonics
• Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment
• Few-mode Field Quantization for Multiple Emitters
• Dynamic of Single Molecules in Collective Light-Matter States from First Principles
• Chiral Polaritonics: Analytic Solutions, Intuition and its Use
• Reduced-density-matrix-based ab initio cavity quantum electrodynamics
• Cavity engineering of solid-state materials without external driving
• Ultrafast collapse of molecular polaritons in photoswitch-nanoantennas at room temperature
• Effective single mode methodology for strongly coupled multimode molecular-plasmon nanosystems
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• High-Contrast Interferometric Imaging of Single-Molecule Dynamics on Optical Fibers
• Density-Functional Tight Binding Meets Maxwell: Unraveling the Mysteries of (Strong) Light-Matter Coupling Efficiently