Quantum electrodynamical density functional theory for generalized Dicke model

TL;DR

This paper develops a quantum electrodynamical density functional theory for a generalized Dicke model, providing new approximations and demonstrating their effectiveness in the ultrastrong coupling regime, with implications for molecules in cavities.

Contribution

It introduces a ground state QEDFT framework for the generalized Dicke model, including new exchange-correlation functionals and analysis of collective effects in molecule-cavity interactions.

Findings

RPA-QEDFT performs excellently in ultrastrong coupling regimes.

The study reveals the importance of collective effects in molecule-cavity interactions.

The proposed functionals accurately capture the scaling of xc energy with number of molecules.

Abstract

We formulate and analyze in detail the ground state quantum electrodynamical density functional theory (QEDFT) for a generalized Dicke model describing a collection of $N$ tight-binding dimers minimally coupled to a cavity photon mode. This model is aimed at capturing essential physics of molecules in quantum cavities in polaritonic chemistry, or quantum emitters embedded in mesoscopic resonators of the circuit QED, and, because of its simplicity, is expected to provide important insights regarding the general QEDFT. We adopt the adiabatic connection formalism and the diagrammatic many-body theory to regularly derive a sequence of explicit approximations for the exchange-correlation (xc) energy in the ground state QEDFT, and to compare their performance with the results of exact numerical diagonalization. Specifically, we analyze the earlier proposed one-photon optimized effective potential (OEP) scheme, its direct second order extensions, and a non-perturbative xc functional based on the photon random phase approximation (RPA). Our results demonstrate the excellent performance of RPA-QEDFT in the ultrastrong coupling regime, and for any number $N$ of Dicke molecules in the cavity. We study in detail the scaling of xc energy with $N$, and emphasize the importance for the ground state QEDFT of collective effects in the interaction of molecules with cavity photons. Finally, we discuss implications of our results for realistic systems.