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

TL;DR

This paper develops a new coupled cluster theory for electron correlation in vibrational strong light-matter coupling, enabling more accurate quantum chemical calculations within cavity environments.

Contribution

It introduces the cavity Born-Oppenheimer coupled cluster (CBO-CC) theory and a hierarchy of linearisation schemes to efficiently model electron correlation under vibrational strong coupling.

Findings

lCRP-CCSD provides results close to self-consistent CRP-CCSD.

Significant differences observed between mean-field and correlated approaches.

Method applied successfully to cavity-modified reactions and microsolvation energies.

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 linearisation 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$+$CH$_3$Br, 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 non-trivial 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.