Cavity Born-Oppenheimer Coupled Cluster Theory: Towards Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime
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arXiv
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| Format: | Preprint |
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2025
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| _version_ | 1866912738941337600 |
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| author | Fischer, Eric W. |
| author_facet | Fischer, Eric W. |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2507_10100 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Cavity Born-Oppenheimer Coupled Cluster Theory: Towards Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime Fischer, Eric W. Chemical Physics 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. |
| title | Cavity Born-Oppenheimer Coupled Cluster Theory: Towards Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2507.10100 |