Cover Image

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...

Full description

Saved in:
Bibliographic Details
Main Authors: Weidman, Jared (Author) , Dadgar, Mohammadhossein (Shahriyar) (Author) , Stewart, Zachary J. (Author) , Peyton, Benjamin G. (Author) , Ulusoy, Inga (Author) , Wilson, Angela K. (Author)
Format: Article (Journal)
Language:English
Published: 7 March 2024
In: The journal of chemical physics
Year: 2024, Volume: 160, Issue: 9, Pages: 1-16
ISSN:1089-7690
DOI:10.1063/5.0188471
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1063/5.0188471
Get full text
Author Notes:Jared D. Weidman, Mohammadhossein (Shahriyar) Dadgar, Zachary J. Stewart, Benjamin G. Peyton, Inga S. Ulusoy, and Angela K. Wilson
Description
Summary: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.
Item Description:Veröffentlicht: 05. März 2024
Gesehen am 12.08.2024
Physical Description:Online Resource
ISSN:1089-7690
DOI:10.1063/5.0188471

Similar Items