2023/08/18 by Sara Angelico, Angelico, Sara, Tor S. Haugland +5 · 3 citations
Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Mechanical and Optical Resonators #Strong Light-Matter Interactions
paper · pdf · doi:10.48550/arxiv.2308.09594
openalex publication_date 2023/08/18 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Chemical and photochemical reactivity, as well as supramolecular organization and several other molecular properties, can be modified by strong interactions between light and matter. Theoretical studies of these phenomena require the separation of the Schrödinger equation into different degrees of freedom as in the Born-Oppenheimer approximation. In this paper, we analyze the electron-photon Hamiltonian within the cavity Born-Oppenheimer approximation (CBOA), where the electronic problem is solved for fixed nuclear positions and photonic parameters. Specifically, we focus on intermolecular interactions in representative dimer complexes. The CBOA potential energy surfaces are compared with those obtained using a polaritonic approach, where the photonic and electronic degrees of freedom are treated at the same level. This allows us to assess the role of electron-photon correlation and the accuracy of CBOA.