Exactly Embedded Wavefunction Methods for Characterizing Nitrogen Reduction Catalysis
Abstract
The final year of research activity witnessed successful completion of the proposed research goals of developing and applying exactly embedded density functional and wavefunction theory methods for the investigation of small-molecular activation catalysis, such as hydrogen and nitrogen reduction. In a significant methodological advance from the past year, we developed an accurate and systematically improvable framework for embedding a correlated wavefunction description of a subsystem in a density functional theory description of the surrounding molecular environment (J. Chem. Phys., 140, 18A507 (2014).). Finally, we applied these newly developed embedding methods to the task of designing new transition-metal catalysts for small-molecule activation. A central challenge in the development of inorganic hydrogen-evolution catalysts is to avoid deleterious coupling of the energetics of metal-site reduction from the kinetics of metal-hydride formation. In work that we are currently preparing for publication, we combined theoretical and experimental methods to investigate a new class of cobalt diimine-dioxime catalysts that shows promise for achieving this aim by introducing an intramolecular proton-shuttle via a pyridyl pendant group.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 15, 2015
- Accession Number
- ADA614249
Entities
People
- Thomas F. Miller Iii
Organizations
- California Institute of Technology