Intermolecular interactions in optical cavities: an ab initio QED study

Journal of Chemical Physics 154,9, 094113 (2021)

Intermolecular interactions in optical cavities: an ab initio QED study

Tor S. Haugland, Christian Schäfer, Enrico Ronca, Angel Rubio, Henrik Koch

Intermolecular bonds are weak compared to covalent bonds, but they are strong enough to influence the properties of large molecular systems. In this work, we investigate how strong light-matter coupling inside an optical cavity can modify these intermolecular forces. We perform a detailed comparison between currently available ab initio electron-photon methodologies. The electromagnetic field inside the cavity can modulate the ground state properties of weakly bound complexes. Controlling the field polarization, the interactions can be stabilized or destabilized, and electron densities, dipole moments, and polarizabilities can be altered. We demonstrate that electron-photon correlation is fundamental to describe intermolecular interactions in strong light-matter coupling. This work proposes optical cavities as a novel tool to manipulate and control ground state properties, solvent effects, and intermolecular interactions for molecules and materials.

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Doi
http://dx.doi.org/10.1063/5.0039256
arxiv
http://arxiv.org/abs/2012.01080
Notes
T.S.H. and H.K. acknowledge computing resources through UNINETT Sigma2 - the National Infrastructure for High Performance Computing and Data Storage in Norway, through project number NN2962k. T.S.H. and H.K. acknowledge funding from the Marie Sk lodowskaCurie European Training Network “COSINE - COmputational Spectroscopy In Natural sciences and Engineering”, Grant Agreement No. 765739, the Research Council of Norway through FRINATEK projects 263110 and 275506. C.S. and A.R. acknowledge support of the RouTe Project (13N14839), financed by the Federal Ministry of Education and Research (Bundesministerium f¨ur Bildung und Forschung (BMBF)), the European Research Council (ERC-2015-AdG694097), the Cluster of Excellence “Advanced Imaging of Matter” (AIM) and Grupos Consolidados (IT1249-19). The Flatiron Institute is a division of the Simons Foundation.

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