Cavity Born–Oppenheimer Coupled Cluster Theory: Toward Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime
Eric W. Fischer
TL;DR
This paper introduces a new method to study electron correlation in chemical reactions under vibrational strong light-matter coupling using a coupled cluster approach.
Contribution
The novel CRP-CCSD method combines cavity reaction potential with coupled cluster theory to model cavity-modified electron correlation.
Findings
lCRP-CCSD methods provide excellent results compared to CRP-CCSD in the few-molecule limit.
Mean-field and correlated results show significant differences in both reactive and collective scenarios.
Electron correlation under vibrational strong coupling is nontrivial and requires beyond-mean-field approaches.
Abstract
We present a detailed derivation and discussion of cavity Born–Oppenheimer coupled cluster (CBO–CC) theory and address cavity-modified electron correlation in the vibrational strong coupling regime. Methodologically, we combine the recently proposed cavity reaction potential (CRP) approach with the Lagrangian formulation of CC theory and derive a self-consistent CRP-CC method at the singles and doubles excitations level (CRP-CCSD). The CRP-CC approach is formally similar to implicit solvation CC models and provides access to the CBO–CC electronic ground state energy minimized in cavity coordinate space on a CC level of theory. A hierarchy of linearization schemes (lCRP-CCSD) similar to canonical CC theory systematically lifts the self-consistent nature of the CRP-CCSD approach and mitigates numerical cost by approximating electron correlation effects in energy minimization. We provide a…
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Taxonomy
TopicsStrong Light-Matter Interactions · Spectroscopy and Quantum Chemical Studies · Perovskite Materials and Applications