Wavefunction Embedding for Molecular Polaritons

Abstract

Polaritonic chemistry relies on the strong light-matter interaction phenomena for altering the chemical reaction rates inside optical cavities. To explain and to understand these processes, the development of reliable theoretical models is essential. While computationally efficient quantum electrodynamics self-consistent field (QED-SCF) methods, such as quantum electrodynamics density functional theory (QEDFT) needs accurate functionals, quantum electrodynamics coupled cluster (QED-CC) methods provide a systematic increase in accuracy but at much greater cost. To overcome this computational bottleneck, herein we introduce and develop the QED-CC-in-QED-SCF projection-based embedding method that inherits all the favorable properties from the two worlds, computational efficiency and accuracy. The performance of the embedding method is assessed by studying some prototypical but relevant reactions, such as methyl transfer reaction, proton transfer reaction, as well as protonation reaction in a complex environment. The results obtained with the new embedding method are in excellent agreement with more expensive QED-CC results. The analysis performed on these reactions indicate that the strong light-matter interaction is very local in nature and that only a small region should be treated at the QED-CC level for capturing important effects due to cavity. This work sets the stage for future developments of polaritonic quantum chemistry methods and it will serve as a guideline for development of other polaritonic embedding models.

References in corpus (13)

• Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
• Quantum embedding theories
• Theoretical Challenges in Polaritonic Chemistry
• Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity
• Intermolecular interactions in optical cavities: an ab initio QED study
• Theory of Photon Condensation in a Spatially-Varying Electromagnetic Field
• Ions in solution: Density Corrected Density Functional Theory (DC-DFT)
• A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity
• Resolution of Gauge Ambiguities in Molecular Cavity Quantum Electrodynamics
• Cavity-modulated ionization potentials and electron affinities from quantum electrodynamics coupled-cluster theory
• Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations
• Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment
• Reduced-density-matrix-based ab initio cavity quantum electrodynamics