Design of Novel Metal Organic Chalcogenolates via High-Throughput Crystal Structure Generation and Density Functional Theory

In this work, we leverage density functional theory (DFT), crystal structure generation, and geometric algorithms to aid in the design and synthesis of low-energy metal organic chalcogenolates (MOChas). MOChas are hybrid organic-inorganic, self-assembled Van der Waals crystals where low-dimensional transition-metal chalcogenide (TMC) inorganic structures are scaffolded by organic ligands, which insulate the TMCs from one another. Despite being bulk crystals, MOChas, like other low-dimensional TMC materials, host excitonic properties relevant to optoelectronic applications. The choice of organic ligand can control the geometry of the inorganic structure, driving the optoelectronic properties of MOChas. This tunability and ease of synthesizability make MOChas a compelling material class for exploring structure-property relationships. However, very few MOChas have been experimentally synthesized, and manual search of the phase and composition space is intractable. We propose a high-throughput workflow for novel MOChas by (i) systematically generating inorganic crystal structures via Ab Initio random structure searching, (ii) matching hypothetical combinations of inorganic structures, organic ligands, and corresponding stacking patterns, and (iii) evaluating their structural feasibility with DFT. With this workflow, we can present a library of energetically favorable MOCha structures for synthesis, some of which have already been produced by our experimental collaborators.