Classification of doubly excited molecular electronic states.

ABSTRACT: Electronic states with partial or complete doubly excited character play a crucial role in many areas, such as singlet fission and non-linear optical spectroscopy. Although doubly excited states have been studied in polyenes and related systems for many years, the assignment as singly vs. doubly excited, even in the simplest case of butadiene, has sparked controversies. So far, no well-defined framework for classifying doubly excited states has been developed, and even more, there is not even a well-accepted definition of doubly excited character as such. Here, we present a solution: a physically motivated definition of doubly excited character based on operator expectation values and density matrices, which works independently of the underlying orbital representation, avoiding ambi

SUBMITTER: do Casal MT 

PROVIDER: S-EPMC10094316 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature