Freiburg 2024 – scientific programme

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MO: Fachverband Molekülphysik

MO 20: Theoretical Molecular Physics

MO 20.4: Talk

Thursday, March 14, 2024, 15:15–15:30, HS 3042

Cavity-Born-Oppenheimer Hartree-Fock: Vibronic-Strong- Coupling beyond a single molecule — •Thomas Schnappinger and Markus Kowalewski — Department of Physics, Stockholm University, Sweden

When a molecule interacts with the vacuum field of a nanoscale cavity, strong coupling reshapes the potential energy surfaces to form hybrid light-matter states called polaritons. Recent experiments show that this strong coupling between light and matter is capable of modifying chemical and physical properties. The situation in which the quantized cavity modes are coupled via their characteristic frequency to vibrational degrees of freedom of molecules is called vibrational strong coupling (VSC). In the VSC regime, the chemistry of a single electronic state (mostly the ground state) and its vibrational spectroscopy are influenced by the cavity interaction. In this theoretical contribution we use the ab-initio Cavity-Born-Oppenheimer-Hartree-Fock approach to study the effect of VSC on the ground state properties of single molecules and small ensembles of such molecules. We are able to optimize cavity-coupled molecular systems and can calculate vibro-polaritonic IR spectra, since we have implemented analytical gradients. Our ab-initio treatment allows us to study the interactions between individual molecules mediated by the cavity. These interactions give rise to local strong coupling effects that allow the modification of chemical reactivity in the VSC context.

Keywords: Vibronic-Strong-Coupling; Strong Light-Matter Coupling; Electronic Structure; Polaritonic Chemistry; ab initio quantum electrodynamics