Wavefunction embedding for molecular polaritons

Polaritonic chemistry relies on the strong light-matter interaction phenomena for altering the chemical reaction rates inside optical cavities. To explain and 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, need 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, and 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 indicates that the electron-photon correlation effects are 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 will serve as a guideline for the development of other polaritonic embedding models. Published under an exclusive license by AIP Publishing.

Automated summary

Polaritonic chemistry relies on strong light-matter interaction phenomena to alter chemical reaction rates, and reliable theoretical models are essential for understanding these processes. This study introduces the QED-CC-in-QED-SCF projection-based embedding method, which combines computational efficiency and accuracy, and evaluates its performance by studying relevant reactions.