ABSTRACT

WIth support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Pere Miró and his research group at the University of South Dakota are using advanced computational approaches to understand the nucleation and growth of functionalized polyoxovanadate-alkoxide clusters, as well as the ability of these clusters to catalyze the reactions of small molecules. The development of molecular catalysts that have the ability to accelerate complex chemical reactions involving many electrons remains a major challenge due to changes that often affect the durability and behavior of such species under harsh reaction conditions. Therefore, understanding and controlling the properties of these catalytic compounds is of fundamental importance, and relies on the ability to manipulate the evolution of transient species in solution. The polyoxovanadate-alkoxide clusters under study here will provide a useful platform better understand fundamental aspects of the synthesis, reactivity, and durability of metal oxide catalysts, in general, as well as the catalytic activation of small molecules. This work will contribute to the long-term goal of the Miró research group to use modern computational methodologies to discover new roadmaps for the nucleation of molecular mimics of catalytic metal-oxide materials. The project includes an educational outreach program involving hands-on workshops at neighboring tribal colleges, the engagement of tribal undergraduate students in science, technology, engineering, and mathematics (STEM) research, and leading National Chemistry Week activities for students at K-12 schools.

Pere Miró and his research team will use high-level quantum chemical calculations and neural network algorithms to examine the nucleation mechanism of first-row functionalized polyoxovanadate-alkoxide clusters--up to the formation of hexameric species--as well as to better understand the impact of dynamic experimental conditions on the structure-redox relationships and multi-electron reactivity of the clusters. Specifically, a combination of density functional theory calculations benchmarked against domain-based local pair natural orbital coupled cluster and second-order complete active space methodologies are being used to characterize nucleation intermediates and derive neural network potentials to streamline the exploration of the nucleation space. This research seeks to enrich the understanding of structure-function relationships that control nucleation and electrocatalytic properties. The scientific broader impacts of this work include transforming the way the organometallic chemistry community views function-oriented synthesis of these species using computational methodologies and to guide the discovery of new functionalities. The project also will provide advanced training opportunities for graduate and undergraduate students, including directed training opportunities for students from groups that are underrepresented in the physical sciences.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

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