title: Modeling molecule-plasmon interactions using quantized radiation fields within time-dependent electronic structure theory.
abstract: We present a combined cavity quantum electrodynamics/ab initio electronic structure approach for simulating plasmon-molecule interactions in the time domain. The simple Jaynes-Cummings-type model Hamiltonian typically utilized in such simulations is replaced with one in which the molecular component of the coupled system is treated in a fully ab initio way, resulting in a computationally efficient description of general plasmon-molecule interactions. Mutual polarization effects are easily incorporated within a standard ground-state Hartree-Fock computation, and time-dependent simulations carry the same formal computational scaling as real-time time-dependent Hartree-Fock theory. As a proof of principle, we apply this generalized method to the emergence of a Fano-like resonance in coupled molecule-plasmon systems; this feature is quite sensitive to the nanoparticle-molecule separation and the orientation of the molecule relative to the polarization of the external electric field.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.
authors.forename: Daniel R
authors.initials: DR
authors.lastname: Nascimento
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.
authors.forename: A Eugene
authors.initials: AE
authors.lastname: DePrince