Experimental and Theoretical Investigations of Organic Reaction Rates and Mechanisms

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In this project, funded by the Chemical Structure, Dynamics, and Mechanisms B Program of the Chemistry Division, Professor K. N. Houk of the UCLA Department of Chemistry and Biochemistry, and Chemical and Biomolecular Engineering will develop new computational methods to understand chemical reactivity, selectivity and mechanisms. This research involves the use of equations of physics, primarily quantum mechanics and molecular dynamics. Intensive computer calculations predict the structures of molecules and the processes by which they transform to products during chemical reactions. The Houk group has pioneered in this area and continues to demonstrate to chemists that computation is a crucial adjunct to their experimental research. As one part of this project, computational models for perovskites are expected to lead to new architectures and additives for enhanced photovoltaic performance. Planned research will involve extensive collaboration with experimental research groups. This research provides for computational underpinning and contributes to the better understanding of new and puzzling experimental results, and provides guidance to experimentalists about new experiments. Broader impacts activities include outreach to students at UCLA, high schools and the general public. Group members participate in outreach to potential STEM students to attract them to the excitement of a career in computational chemistry. The participants supported by this grant continue to be active members of the Organization for Cultural Diversity in Science (OCDS) at UCLA.The Houk group has pioneered the study of ambimodal reactions that can form several products from one transition state. This continuing project will develop concepts to understand reactivities and mechanisms for organic reactions, and to improve computational methods for quantitative calculations of reaction rates and mechanisms. This project involves calculations of reaction paths and molecular dynamics of organic reactions, including reactions in solution. Various methods to analyze reactivity, such as the distortion/interaction model of reactivity that was conceived and developed in the Houk lab, will be applied to organic reactions and mechanisms, selectivities of organometallic reactions, and molecular dynamics of reactions in solution. Analyses and design of new perovskite photovoltaics will be performed. New approaches to understanding chemical reactivity will be developed. Collaborations on mechanisms and selectivities with experimental research groups are expected to provide explanations and guide future research directions. This project will have a significant component dedicated to the computational study of newly discovered, organic and organometallic reactions. New methods will be developed and shared with the general chemical community. Predictions of new chemistry will be studied by collaborators. Broader impacts of this research include training of future leaders of organic computation and theory, teaching the chemical community how to solve problems with computation, as well as teaching theoreticians how to communicate with experimentalists. The highly collaborative environment of this research is a significant benefit to the researchers engaged in this science. Undergraduates, graduate students, and postdoctorals will be trained in the use of theory and computation as a companion to experiment for the solution of chemical problems.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.