Perturbation theoretical approaches to strong light-matter coupling in ground and excited electronic states for the description of molecular polaritons

• Verfasst von: Bauer, Marco [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Perturbation theoretical approaches to strong light-matter coupling in ground and excited electronic states for the description of molecular polaritons
• Verf.angabe: Marco Bauer and Andreas Dreuw
• E-Jahr: 2023
• Jahr: 31 March 2023
• Umfang: 13 S.
• Fussnoten: Gesehen am 16.05.2023
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2023
• Band/Heft Quelle: 158(2023), 12 vom: März, Artikel-ID 124128, Seite 1-13
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/5.0142403
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1845502485

Abstract

Quantum chemical methods for the description of molecular polaritonic states in the strong coupling regime based on the Pauli-Fierz Hamiltonian are introduced. Based on a quantum electrodynamic Hartree-Fock (QED-HF) reference, a QED Møller-Plesset perturbation theory of second order for the electronic ground state and a second order quantum electrodynamic algebraic diagrammatic construction scheme for the polarization propagator [QED-ADC(2)] for excited electronic states have been derived, implemented, and tested for polaritons in hydrogen fluoride. Analogous approaches based on a standard non-polaritonic HF reference are also presented and thoroughly compared, both algebraically and numerically, to those based on the QED-HF reference. Furthermore, a promising route to approximate QED-ADC methods based on a unitary transformation of the algebraic expression into a restricted state space is outlined showing excellent agreement in second order with QED-ADC(2). All presented novel methods are compared to and tested against other existing ab initio approaches, mostly QED coupled cluster theory, including single and double excitations, and show qualitative agreement at a reduced computational effort.