Extending the Tavis-Cummings model for molecular ensembles -- Exploring the effects of dipole self energies and static dipole moments

Abstract

Strong coupling of organic molecules to the vacuum field of a nanoscale cavity can be used to modify their chemical and physical properties. We extend the Tavis-Cummings model for molecular ensembles and show that the often neglected interaction terms arising from the static dipole moment and the dipole self-energy are essential for a correct description of the light-matter interaction in polaritonic chemistry. On the basis of a full quantum description, we simulate the excited-state dynamics and spectroscopy of MgH${}^{+}$ molecules resonantly coupled to an optical cavity. We show that the inclusion of static dipole moments and the dipole self-energy is necessary to obtain a consistent model. We construct an efficient two-level system approach that reproduces the main features of the real molecular system and may be used to simulate larger molecular ensembles.

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Cited by in corpus (5)

• Disentangling collective coupling in vibrational polaritons with double quantum coherence spectroscopy
• Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
• The role of dark polariton states for electronic strong coupling in molecules
• Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons
• Density-functional theory for the Dicke Hamiltonian