Characterizing Bonding Patterns in Diradicals and Triradicals by Density-Based Wave Function Analysis: A Uniform Approach

• DOI: 10.1021/acs.jctc.7b01012
• Publication Date: 2017-12-21T23:13:33Z
• Authors: Natalie Orms; Dirk R. Rehn; Andreas Dreuw; Anna I. Krylov
• Keywords: Unpaired electron

Density-based wave function analysis enables unambiguous comparisons of the electronic structure computed by different methods and removes ambiguity orbital choices. We use this tool to investigate performance spin-flip for several prototypical diradicals triradicals. In contrast previous calibration studies that focused on energy gaps between high- low spin-states, we focus properties underlying functions, such as number effectively unpaired electrons. Comparison density functional theory results provides insight into when applied strongly correlated systems polyradicals. show canonical molecular orbitals species like large copper-containing fail correctly represent due highly non-Koopmans character, while density-based same delivers a clear picture bonding pattern.