Do Molecular Geometries Change Under Vibrational Strong Coupling?
arXiv:2405.17246 · doi:10.1021/acs.jpclett.4c01810
Abstract
As pioneering experiments have shown, strong vibrational coupling between molecular vibrations and light modes in an optical cavity can significantly alter molecular properties and even affect chemical reactivity. However, the current theoretical description is limited and far from complete. To explore the origin of this exciting observation, we investigate how the molecular structure changes under strong light-matter coupling using an ab-initio method based on the cavity Born-Oppenheimer Hartree-Fock ansatz. By optimizing HO and HO resonantly coupled to cavity modes, we study the importance of reorientation and geometric relaxation. In addition, we show that the inclusion of one or two cavity modes can change the observed results. On the basis of our findings, we derive a simple concept to estimate the effect of the cavity interaction on the molecular geometry using the molecular polarizability and the dipole moments.
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Cited by in corpus (3)
- Molecular Polarizability under Vibrational Strong Coupling
- Cavity-modified electronic interactions in molecular ensembles under vibrational strong coupling: Combined insights from cavity Born-Oppenheimer perturbation and ab initio wave function theories
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