Capturing the most important properties of complex systems, the concepts of “reactive functional groups” and “active site” play a crucial role in the analysis of various phenomena and processes in chemistry, biology and materials science. Frontier molecular orbitals (FMOs) have achieved success in the application of small systems, but the delocalization nature makes them difficult to highlight the active sites for large systems. Therefore, only the proper combination of both “frontier” and “localized” factors can effectively reflects the chemical nature of a complex system. Here, we seek to explore this possibility from orbitalets that are localized in both physical and energy spaces, and propose the concept of frontier molecular orbitalets (FMOLs). With both energy and location information, FMOLs are able to locate the area with the greatest chemical reactivity of a system. Through testing, we find that FMOLs can clearly show the interactions between chemical fragments in various systems. They can be applied to analyze complicated phenomena like charge transfer, and provide a rapid way to analyze chemical reactions from the transition state. All the tests demonstrate that FMOLs can identify the chemical nature of complex systems in an easily understandable way, making them useful in various applications.

Describing chemical properties with frontier molecular orbitalets

ACS Fall 2021

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