Bonn 2025 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 2: Polaritonic Effects in Molecular Systems I (joint session MO/Q)
MO 2.4: Vortrag
Montag, 10. März 2025, 11:45–12:00, HS XV
Analytic model reveals local molecular polarizability changes induced by collective VSC — •Jacob Horak1,2, Dominik Sidler1,2,3, Thomas Schnappinger4, Michael Ruggenthaler1,2, and Angel Rubio1,2,5 — 1Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany — 2The Hamburg Center for Ultrafast Imaging, Hamburg, Germany — 3Paul Scherrer Institut, Villigen, Switzerland — 4Stockholm University, Stockholm, Sweden — 5The Flatiron Institute, New York, USA
Despite recent numerical evidence, one of the fundamental theoretical mysteries of polaritonic chemistry is how and if collective strong coupling can induce local changes of the electronic structure to modify chemical properties. Here we present non-perturbative analytic results for a model system consisting of an ensemble of N harmonic molecules under vibrational strong coupling (VSC) that alters our present understanding of this fundamental question. We discover that the electronic molecular polarizabilities are modified even in the case of vanishingly small single-molecule couplings. Consequently, this non-perturbative local polarization mechanism persists even in the large-N limit. In contrast, a perturbative calculation of the polarizabilities leads to a qualitatively erroneous scaling behavior with vanishing effects in the large-N limit. Our fundamental theoretical observations demonstrate that hitherto existing collective-scaling arguments are insufficient for polaritonic chemistry / physics.
Keywords: Polarizability; cavity; strong coupling; polaritonic