Cavity-modified molecular dipole switching dynamics
Polaritonic states, which are formed by resonances between a molecular excitation and the photonic mode of a cavity, have a number of useful properties that offer new routes to control molecular photochemistry using electric fields. To provide a theoretical description of how polaritonic states affe...
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| Hauptverfasser: | , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
7 March 2024
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| In: |
The journal of chemical physics
Year: 2024, Jahrgang: 160, Heft: 9, Pages: 1-16 |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/5.0188471 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1063/5.0188471
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| Verfasserangaben: | Jared D. Weidman, Mohammadhossein (Shahriyar) Dadgar, Zachary J. Stewart, Benjamin G. Peyton, Inga S. Ulusoy, and Angela K. Wilson |
| Zusammenfassung: | Polaritonic states, which are formed by resonances between a molecular excitation and the photonic mode of a cavity, have a number of useful properties that offer new routes to control molecular photochemistry using electric fields. To provide a theoretical description of how polaritonic states affect the real-time electron dynamics in molecules, a new method is described where the effects of strong light-molecule coupling are implemented using real-time electronic structure theory. The coupling between the molecular electronic states and the cavity is described by the Pauli-Fierz Hamiltonian, and transitions between polaritonic states are induced via an external time-dependent electric field using time-dependent configuration interaction (TDCI) theory, producing quantum electrodynamics TDCI (QED-TDCI). This method is used to study laser-induced ultrafast charge transfer and dipole-switching dynamics of the LiCN molecule inside a cavity. The increase in cavity coupling strength is found to have a significant impact on the energies and transition dipole moments of the molecule-cavity system. The convergence of the polaritonic state energies as a function of the number of included electronic and photonic basis states is discussed. |
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| Beschreibung: | Veröffentlicht: 05. März 2024 Gesehen am 12.08.2024 |
| Beschreibung: | Online Resource |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/5.0188471 |