Quantum Chemistry Calculations of Circularly Polarized Luminescence (CPL): From Spectral Modeling to Molecular Design

Circularly polarized luminescence (CPL)─the emission of circularly polarized light from luminescent chiral nonracemic matter─has garnered unprecedented attention in the past decade. Once a niche technique used for the characterization of excited states, CPL has evolved to a powerful and widespread tool for developing functional materials with multiple applications. The development of novel CPL emitters is costly and time-consuming because the key CPL quantities (dissymmetry factor, g_lum, and CPL brightness, B_CPL) often elude simple structure-to-property relationships based on existing knowledge. Today, research in the field is aided by quantum chemistry calculations which offer insight into CPL properties and serve as a predictive tool for the rational design of efficient CPL-active materials. The present review is divided into three sections: (1) a comprehensive presentation of the theoretical foundation of CPL calculations, electronic structure description, environment effects, vibronic modulation, band shape broadening, and aggregate simulation; (2) an extensive literature survey, organized according to a structural criterion; and (3) a critical reassessment of literature data, accompanied by a statistical analysis, aimed at offering the best practices for accurate CPL calculations and identifying the key structural and electronic features that enable the simulation-guided design of novel CPL emitters.