2025/03/21 by Thomas Schnappinger, Markus Kowalewski · 1 voice · 8 citations
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical physics #Chemistry #Computational chemistry #Computer science #Coupling (piping) #Materials science #Molecular physics #Molecule #Physics #Polarizability #Quantum mechanics #Spectroscopy and Quantum Chemical Studies #Strong Light-Matter Interactions #physics.chem-ph
paper · pdf · doi:10.1021/acs.jctc.5c00461
published in Journal of Chemical Theory and Computation 21(10), 5171-5181 (American Chemical Society)
arxiv published 2025/03/21 · arxiv updated 2025/03/21 · openalex publication_date 2025/05/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
Polaritonic chemistry offers the possibility of modifying molecular properties and even influencing chemical reactivity through strong coupling between vibrational transitions and confined light modes in optical cavities. Despite considerable theoretical progress, and due to the complexity of the coupled light-matter system, the fundamental mechanism of how and if collective strong coupling can induce local changes in individual molecules is still unclear. We derive an analytical formulation of static polarizabilities within linear-response theory for molecules under strong coupling using the cavity Born-Oppenheimer Hartree-Fock ansatz. This ab-initio method consistently describes vibrational strong coupling and electron-photon interactions even for ensembles of molecules. For different types of molecular ensembles, we observed local changes in the polarizabilities and dipole moments that are induced by collective strong coupling. Furthermore, we used the polarizabilities to calculate vibro-polaritonic Raman spectra in the harmonic approximation. This allows us to comprehensively compare the effect of vibrational strong coupling on IR and Raman spectra on an equal footing.