Cavity Born–Oppenheimer Coupled Cluster Theory: Toward Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime

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 thorough comparison of CRP-CCSD, lCRP-CCSD, and CRP-Hartee-Fock methods for a cavity-modified Menshutkin reaction, pyridine+CH3Br, and cavity-induced collective electronic effects in microsolvation energies of selected methanol–water clusters. We find lCRP-CCSD methods to provide excellent results compared to the self-consistent CRP-CCSD approach in the few-molecule limit. We furthermore observe significant differences between mean-field and correlated results in both reactive and collective scenarios. Our work emphasizes the nontrivial character of electron correlation under vibrational strong coupling and provides a starting point for further developments in ab initio vibro-polaritonic chemistry beyond the mean-field approximation.