Realistic Ab Initio Predictions of Excimer Behavior under Collective Light-Matter Strong Coupling DOI Creative Commons
Matteo Castagnola, Marcus T. Lexander, Henrik Koch

и другие.

Physical Review X, Год журнала: 2025, Номер 15(2)

Опубликована: Май 5, 2025

Experiments show that light-matter strong coupling affects chemical properties, though the underlying mechanism remains unclear. A major challenge is to perform reliable and affordable simulation of molecular behavior when many molecules are collectively coupled same optical mode. This paper presents an quantum electrodynamics cluster method for collective regime. The model describes electronic electron-photon correlation within a subsystem, while simplified description polaritonic excitations allows realistic microscopic coupling. developed framework provides computationally tractable route accurately simulate molecule in environment, which unfeasible several treated explicitly. We investigate properties argon dimer under In single-molecule regime (large coupling), potential energies substantially modified, weakening excimer bond. contrast, (small coupling, large number molecules), ground state energy surface first vibrational levels excited do not change significantly. However, produces abrupt transition landscape excimer, causing higher behave similarly vibrations state. expect formation be inhibited by conclude altered via distinct mechanisms regimes. also discuss fundamental aspects chemistry, such as resonance conditions sudden changes critical strength achieved. Published American Physical Society 2025

Язык: Английский

Strong Coupling Møller–Plesset Perturbation Theory DOI Creative Commons

Yassir El Moutaoukal,

Rosario R. Riso, Matteo Castagnola

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Март 31, 2025

Perturbative approaches are methods to efficiently tackle many-body problems, offering both intuitive insights and analysis of correlation effects. However, their application systems where light matter strongly coupled is nontrivial. Specifically, the definition suitable orbitals for zeroth-order Hamiltonian represents a significant theoretical challenge. While reviewing previously investigated orbital choices, this work presents an alternative polaritonic basis strong coupling regime. We develop quantum electrodynamical (QED) Møller–Plesset perturbation theory using obtained from QED Hartree–Fock. assess strengths limitations different with emphasis on frequency strength dispersions, intermolecular interactions polarization orientational The results show essential role consistent molecular framework in order achieve accurate description cavity-induced electron−photon

Язык: Английский

Процитировано

2
Realistic Ab Initio Predictions of Excimer Behavior under Collective Light-Matter Strong Coupling DOI Creative Commons
Matteo Castagnola, Marcus T. Lexander, Henrik Koch

и другие.

Physical Review X, Год журнала: 2025, Номер 15(2)

Опубликована: Май 5, 2025

Experiments show that light-matter strong coupling affects chemical properties, though the underlying mechanism remains unclear. A major challenge is to perform reliable and affordable simulation of molecular behavior when many molecules are collectively coupled same optical mode. This paper presents an quantum electrodynamics cluster method for collective regime. The model describes electronic electron-photon correlation within a subsystem, while simplified description polaritonic excitations allows realistic microscopic coupling. developed framework provides computationally tractable route accurately simulate molecule in environment, which unfeasible several treated explicitly. We investigate properties argon dimer under In single-molecule regime (large coupling), potential energies substantially modified, weakening excimer bond. contrast, (small coupling, large number molecules), ground state energy surface first vibrational levels excited do not change significantly. However, produces abrupt transition landscape excimer, causing higher behave similarly vibrations state. expect formation be inhibited by conclude altered via distinct mechanisms regimes. also discuss fundamental aspects chemistry, such as resonance conditions sudden changes critical strength achieved. Published American Physical Society 2025

Язык: Английский

Процитировано

1