Local operator partitioning of electronic energy for electronic energy transfer: An efficient algorithm

An efficient computational algorithm to implement a local operator approach to partitioning electronic energy in general molecular systems is presented. This approach, which rigorously defines the electronic energy on any subsystem within a molecule, gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. We apply the technique to the 9-((1-naphthyl)-methyl)-anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH₂-naphthyl groups as subsystems, and examine their electronic energies and populations for several excited states using Configuration Interaction Singles method. The implemented approach shows a wide variety of different behaviors amongst these excited electronic states.