[Article] Prospecting Lighting Applications with Ligand Field Tools and Density Functional Theory: A First-Principles Account of the 4f7− 4f65d1 Luminescence of CsMgBr3:Eu2+

The most efficient way to provide domestic lighting nowadays is by light-emitting diodes (LEDs) technology combined with phosphors shifting the blue and UV emission toward a desirable sunlight spectrum. A route in the quest for warm-white light goes toward the discovery and tuning of the lanthanide-based phosphors, a difficult task, in experimental and technical respects. A proper theoretical approach, which is also complicated at the conceptual level and in computing efforts, is however a profitable complement, offering valuable structure−property rationale as a guideline in the search of the best materials. The Eu2+-based systems are the prototypes for ideal phosphors, exhibiting a wide range of visible light emission. Using the ligand field concepts in conjunction with density functional theory (DFT), conducted in nonroutine manner, we develop a nonempirical procedure to investigate the 4f7−4f65d1 luminescence of Eu2+ in the environment of arbitrary ligands, applied here on the CsMgBr3:Eu2+-doped material. Providing a salient methodology for the extraction of the relevant ligand field and related parameters from DFT calculations and encompassing the bottleneck of handling large matrices in a model Hamiltonian based on the whole set of 33 462 states, we obtained an excellent match with the experimental spectrum, from first-principles, without any fit or adjustment. This proves that the ligand field density functional theory methodology can be used in the assessment of new materials and rational property design.