Three-Electron Dynamics of the Interparticle Coulombic Decay in Doubly Excited Clusters with One-Dimensional Continuum Confinement

Abstract

A detailed analysis of the electronic structure and decay dynamics in a symmetric system with three electrons in three linearly aligned binding sites representing quantum dots (QDs) is given. The two outer A QDs are two-level potentials and can act as (virtual) photon emitters, whereas the central B QD can be ionized from its one level into a continuum confined on the QD axis upon absorbing virtual photons in the inter-Coulombic decay (ICD) process. Two scenarios in such an ABA array are explored. One ICD process is from a singly excited resonance state, whose decay releasing one virtual photon we find superimposed with resonance energy transfer among both A QDs. Moreover, the decay-process manifold for a doubly excited (DE) resonance is explored, in which collective ICD among all three sites and excited ICD among the outer QDs engage. Rates for all processes are found to be extremely low, although ICD rates with two neighbors are predicted to double compared to ICD among two sites only. The slowing is caused by Coulomb barriers imposed from ground or excited state electrons in the A sites. Outliers occur on the one hand at short distances, where the charge transfer among QDs mixes the possible decay pathways. On the other hand, we discovered a shape resonance-enhanced DE-ICD pathway, in which an excited and localized B* shape resonance state forms, which is able to decay quickly into the final ICD continuum.