Wavefunction Embedding for Molecular Polaritons

TL;DR

This paper introduces a novel QED-CC-in-QED-SCF embedding method that combines efficiency and accuracy for modeling molecular polaritons, enabling better understanding of cavity-induced chemical reactions.

Contribution

The development of a projection-based embedding method that integrates QED-CC and QED-SCF approaches for efficient and accurate polaritonic chemistry simulations.

Findings

The embedding method achieves results in excellent agreement with full QED-CC calculations.

Strong light-matter interactions are highly localized, requiring only small regions to be treated at the QED-CC level.

The method facilitates studying complex reactions with reduced computational cost.

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.