Understanding Structure-Function Relationships of Polyoxovanadate-Alkoxide Clusters from a Bottom-Up Perspective

Our group is interested in the computational exploration of the chemical space of molecular metal oxides towards the identification of key structure-function relationships relevant to their speciation, nucleation roadmaps, and overall physicochemical properties. In 2022, our group was awarded NSF's Faculty Early Career Development Program (CAREER) to expand our understanding of structure-function relationships in polyoxovanadate-alkoxide (POV-alkoxide) clusters from a bottom-up perspective. This project uses advanced computational approaches to understand the nucleation and growth of functionalized POV-alkoxide clusters, as well as the ability of these clusters to activate small molecules. We use high-level quantum chemical calculations and neural network algorithms to examine the nucleation mechanism of first-row functionalized POV-alkoxide clusters 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. The scientific 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. Furthermore, this project provides advanced training opportunities for graduate and undergraduate students, including directed training opportunities for students from groups that are underrepresented in the physical sciences (hands-on workshops at neighboring tribal colleges, the engagement of tribal undergraduate students in STEM research, and National Chemistry Week activities for students at K-12 schools).

Lanthanide and Actinide Molecular Metal Oxides

Our group is interested in heavy element chemistry specifically the nucleation and speciation of lanthanide and low valent An(IV) metal oxides in aqueous and non-aqueous media. In this aspect, we are part of a collaborative DOE proposal aimed to transform critical materials separations through metal-oxo cluster chemistry.

Machine Learning and Dynamic Chemical Speciation Networks