Understanding the polaritonic ground state in cavity quantum electrodynamics DOI
Tor S. Haugland, John P. Philbin, Tushar K. Ghosh

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(19)

Published: May 16, 2025

Molecular polaritons arise when molecules interact so strongly with light that they become entangled each other. This light–matter hybridization alters the chemical and physical properties of molecular system allows reactions to be controlled without use external fields. We investigate impact strong coupling on electronic structure using perturbative approaches demonstrate Rayleigh–Schrödinger perturbation theory can reproduce ground state energies in optical cavities comparable accuracy as ab initio cavity quantum electrodynamics methodologies for currently relevant strengths. The method is effective both low high frequency regimes straightforward implement via response functions. Furthermore, we establish simple relations between cavity-induced intermolecular forces van der Waals forces. These findings provide valuable insight into manipulation ground-state polaritonic energy landscapes, shedding systems conditions which modifications achieved.

Language: Английский

Strong Coupling Quantum Electrodynamics Hartree–Fock Response Theory DOI Creative Commons
Matteo Castagnola, Rosario R. Riso,

Yassir El Moutaoukal

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

The development of reliable ab initio methods for light-matter strong coupling is necessary a deeper understanding molecular polaritons. recently developed quantum electrodynamics Hartree-Fock model (SC-QED-HF) provides cavity-consistent orbitals, overcoming several difficulties related to the simpler QED-HF wave function. In this paper, we further develop method by implementing response theory SC-QED-HF. We compare derived linear equations with time-dependent and discuss validity equivalence relations connecting matter electromagnetic observables. Our results show that electron-photon correlation induces an excitation redshift compared energies, effect dipole self-energy on ground excited state properties different basis sets.

Language: Английский

Citations

0
Understanding the polaritonic ground state in cavity quantum electrodynamics DOI
Tor S. Haugland, John P. Philbin, Tushar K. Ghosh

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(19)

Published: May 16, 2025

Molecular polaritons arise when molecules interact so strongly with light that they become entangled each other. This light–matter hybridization alters the chemical and physical properties of molecular system allows reactions to be controlled without use external fields. We investigate impact strong coupling on electronic structure using perturbative approaches demonstrate Rayleigh–Schrödinger perturbation theory can reproduce ground state energies in optical cavities comparable accuracy as ab initio cavity quantum electrodynamics methodologies for currently relevant strengths. The method is effective both low high frequency regimes straightforward implement via response functions. Furthermore, we establish simple relations between cavity-induced intermolecular forces van der Waals forces. These findings provide valuable insight into manipulation ground-state polaritonic energy landscapes, shedding systems conditions which modifications achieved.

Language: Английский

Citations

0