We extend our previous quantum many-body Green's function formalism to characterize the deformations induced in the electronic structure of a quantum emitter when it strongly couples with a plasmon-supporting environment at finite frequency. Through infinite-order perturbation theory, we predict the emergence of subtle yet observable changes in the plasmon-dressed molecule's frontier orbitals, orbital energies, and low-lying electronic excitations when the molecular and plasmonic systems are resonantly coexcited. These distortions, which predominately arise from the finitefrequency image interaction, point to new chemical and optical properties beyond those of the vacuum molecule and bear impact upon resonant plasmon-enhanced molecular spectroscopies and hot-electron-driven chemical catalysis. We propose an experiment capable of testing our predictions.
A simple, easily implemented, accurate, and efficient approximation of long-range electron-electron-repulsion and electron-nucleus-attraction integrals is proposed. It replaces each product of two atomic-orbital (AO) basis functions of an electron by a point charge centered at the midpoint of the two AO's. The magnitude of the point charge is equal to the overlap integral of the two AO's. Each integral is then rapidly evaluated in the direct algorithm as a Coulomb interaction between two point charges. This scheme is implemented in ab initio Hartree-Fock crystalline orbital theory and tested for one-, two-, and three-dimensional solids of metallic, semimetallic, and nonmetallic electronic structures, in which the lattice sums of the direct Coulomb and/or exchange interactions are expected to be slowly convergent. It is shown that this approximation reduces operation and/or memory costs by up to an order of magnitude to achieve converged lattice sums, although the scaling (size dependence) of operation cost is unchanged. An improved criterion for truncating the exchange lattice sum is also proposed.
Finite-temperature coupled-cluster, many-body perturbation, and restricted and unrestricted Hartree-Fock study on one-dimensional solids: Luttinger liquids, Peierls transitions, and spin-and charge-density waves
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