Simple Exchange-Correlation Energy Functionals for Strongly Coupled Light-Matter Systems based on the Fluctuation-Dissipation Theorem

Abstract

Recent experimental advances in strongly coupled light-matter systems has sparked the development of general ab-initio methods capable of describing interacting light-matter systems from first principles. One of these methods, quantum-electrodynamical density-functional theory (QEDFT), promises computationally efficient calculations for large correlated light-matter systems with the quality of the calculation depending on the underlying approximation for the exchange-correlation functional. So far no true density-functional approximation has been introduced limiting the efficient application of the theory. In this paper, we introduce the first gradient-based density functional for the QEDFT exchange-correlation energy derived from the adiabatic-connection fluctuation-dissipation theorem. We benchmark this simple-to-implement approximation on small systems in optical cavities and demonstrate its relatively low computational costs for fullerene molecules up to C${}_{180}$ coupled to 400,000 photon modes in a dissipative optical cavity. This work now makes first principle calculations of much larger systems possible within the QEDFT framework effectively combining quantum optics with large-scale electronic structure theory.

arXiv comment7 pages, 2 figures

References in corpus (26)

• Perspective on density functional theory
• Real-space grids and the Octopus code as tools for the development of new simulation approaches for electronic systems
• Octopus, a computational framework for exploring light-driven phenomena and quantum dynamics in extended and finite systems
• Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
• Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States
• Time-dependent density functional theory for many-electron systems interacting with cavity photons
• Weak and Strong coupling regimes in plasmonic-QED
• Manipulating matter with strong coupling: harvesting triplet excitons in organic exciton microcavities
• Kohn-Sham Approach to Quantum Electrodynamical Density Functional Theory: Exact Time-Dependent Effective Potentials in Real Space
• Optimized Effective Potential for Quantum Electrodynamical Time-Dependent Density Functional Theory
• Intermolecular interactions in optical cavities: an ab initio QED study
• Light-Matter Response in Non-Relativistic Quantum Electrodynamics: Quantum Modifications of Maxwell's Equations
• Ab-initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground state
• Electric dipole polarizabilities at imaginary frequencies for the alkali-metal, alkaline-earth, and inert gas atoms
• Dispersion interactions from a local polarizability model
• Coherent dynamics in cavity femtochemistry: application of the multi-configuration time-dependent Hartree method
• Polaritonic Coupled-Cluster Theory
• Cavity-modulated ionization potentials and electron affinities from quantum electrodynamics coupled-cluster theory
• Light-Matter Interactions via the Exact Factorization Approach
• Variational theory of non-relativistic quantum electrodynamics
• Weak-to-Strong Light-Matter Coupling and Dissipative Dynamics from First Principles
• Shedding Light on Correlated Electron-Photon States using the Exact Factorization
• Conserving approximations in cavity quantum electrodynamics: Implications for density functional theory of electron-photon systems
• Unifying microscopic and continuum treatments of van der Waals and Casimir interactions
• Ultrafast Thermal Modification of Strong Coupling in an Organic Microcavity
• Macroscopic QED - concepts and applications

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