Ab-initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground state

Physical Review B (submitted), (2017)

Ab-initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground state

Johannes Flick, Christian Schäfer, Michael Ruggenthaler, Heiko Appel, Angel Rubio

We introduce a simple scheme to eciently compute photon exchange-correlation contributions due to the coupling to transversal photons as formulated in the newly developed quantumelectrodynamical density functional theory (QEDFT) [1{5]. Our construction employs the optimized-e ective potential (OEP) approach by means of the Sternheimer equation to avoid the explicit calculation of unoccupied states. We demonstrate the eciency of the scheme by applying it to an exactly solvable GaAs quantum ring model system, a single azulene molecule, and chains of sodium dimers, all located in optical cavities and described in full real space. While the rst example is a two-dimensional system and allows to benchmark the employed approximations, the latter two examples demonstrate that the correlated electron-photon interaction appreciably distorts the ground-state electronic structure of a real molecule. By using this scheme, we not only construct typical electronic observables, such as the electronic ground-state density, but also illustrate how photon observables, such as the photon number, and mixed electron-photon observables, e.g. electron-photon correlation functions, become accessible in a DFT framework. This work constitutes the rst three-di ensional ab-initio calculation within the new QEDFT formalism and thus opens up a new computational route for the ab-initio study of correlated electron-photon systems in quantum cavities.

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We would like to thank Claudiu Genes, Camilla Pellegrini,and Ilya V. Tokatly for insightful discussions and acknowledge nancial support from the European Research Council (ERC-2015-AdG-694097), by the European Union's H2020 program under GA no.676580 (NOMAD), and the Austrian Science Fund (FWF P25739-N27).

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