Communication: Exciton analysis in time-dependent density functional theory: How functionals shape excited-state characters

摘要

Excited-state descriptors based on the one-particle transition density matrix referring to the exciton picture have been implemented for time-dependent density functional theory. State characters such as local, extended pi pi*, Rydberg, or charge transfer can be intuitively classified by simple comparison of these descriptors. Strong effects of the choice of the exchange-correlation kernel on the physical nature of excited states can be found and decomposed in detail leading to a new perspective on functional performance and the design of new functionals. (C) 2015 AIP Publishing LLC.