RUI: A Theoretical Investigation of Multireference Diradical Molecules

University Of Richmond, Richmond VA

Investigators

Abstract

Carol Parish of the University of Richmond is supported by a Research in Undergraduate Institutions (RUI) award from the Theoretical and Computational Chemistry program for theoretical investigations of cyclization reactions involving radical intermediates. The work is focused on 1) Utilizing and comparing the Spin-Flip, Singlet-type Strongly Orthogonal Geminal (SSG), Multireference Averaged-Quadratic Coupled Cluster (MR-AQCC) and Completely Renormalized Coupled Cluster (CR-CC(2,3)) methods for describing the multireference character, energies and structures of diradicals; 2) Applying one or more of these methods to the characterization of novel electro-cyclization reactions involving diradical intermediates; 3) Investigating reactions involving tetraradicals; 4) Using the force field based hybrid Monte Carlo-Low Mode method of conformational analysis to evaluate the ensemble of structures for larger natural product diradical precursors; 5) Developing algorithms for using Kohonen's self-organizing map to evaluate the geometrical clustering properties of ensembles, and; 6) Employing the KNIME scripting language to provide "wrappers" to facilitate the use of these methods by undergraduates. The ability to characterize properly open-shell radical species and the corresponding investigation of novel cyclization reactions holds significant promise for advancing the fields of multireference theoretical chemistry, mechanistic organic chemistry, materials design and drug optimization. This work is contributing to furthering understanding of radical behavior and is expected to positively impact these fields of application. The work is being performed by undergraduate researchers as early as their first year of study. The students are receiving intensive training in computational chemistry, and, from this experience, are developing skill sets that will serve them well in their post-baccalaureate scientific careers. The PI is a founding member of the MERCURY consortium which was designed to mentor new computational and theoretical chemistry faculty at other predominately undergraduate institutions in achieving teaching and research excellence. Students involved in this project are participating in MERCURY activities, further broadening the impact of this project.