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We focus on the development and application of new electronic structure theories. Specifically, we are interested in multi-scale models, which allow for the study of large and extended systems. We are developing quantum-embedding theories, which treat different regions of the system at different levels of accuracy. This allows for a high chemical accuracy in a small region, such as an active site of a catalyst, and a less accurate, but more computationally efficient description of the remainder. These tools can then be used to perform first-principle studies on large, reactive, and condensed phase systems. We are interested in applying these methods to metalloenzymes, heterogeneous catalysts, and metal-organic frameworks.

Recent Publications and News Items

On the Mechanism of Ti-Catalyzed Oxidative Nitrene Transfer in [2+2+1] Pyrrole Synthesis from Alkynes and Azobenzen
A combined computational and experimental study on the mechanism of Ti-catalyzed formal [2 + 2 + 1] pyrrole synthesis from alkynes and aryl diazenes is reported. This reaction proceeds through a formally TiII/TiIV redox catalytic cycle as determined by natural bond orbital (NBO) and intrinsic bond orbital (IBO) analysis. Kinetic analysis of the reaction of internal alkynes with azobenzene reveals a complex equilibrium involving Ti═NPh monomer/dimer equilibrium and Ti═NPh + alkyne [2 + 2] cycloaddition equilibrium along with azobenzene and pyridine inhibition equilibria prior to rate-determining second alkyne insertion.

Zachary W Davis-Gilbert, Xuelan Wen, Jason D. Goodpaster, and Ian A. Tonks, "On the Mechanism of Ti-Catalyzed Oxidative Nitrene Transfer in [2+2+1] Pyrrole Synthesis from Alkynes and Azobenzene", J. Am. Chem. Soc. Just Accepted Manuscript

Mechanism of Catalysis

Projection-Based Correlated Wave Function in Density Functional Theory Embedding for Periodic Systems
We present a level shift projection operator-based embedding method for systems with periodic boundary conditions—where the “active” subsystem can be described using either density functional theory (DFT) or correlated wave function (WF) methods and the “environment” is described using DFT.

Dhabih, C.V.; Goodpaster, J.D.  J. Chem. Theory Comput., 2018, ASAP. 

Periodic Wave Function in DFT

Localized Level-Shift Wave Function in DFT Embedding
Huzinaga level-shift projection operator based DFT embedding

Chulhai, D.V.; Goodpaster, J.D.  J. Chem. Theory Comput., 2017, 13(4), 1503–1508. 

Energy splitting

Breaking the Correlation between Energy Costs and Kinetic Barriers in Hydrogen Evolution via a Cobalt Pyridine-Diimine-Dioxime Catalyst

P. Huo, C. Uyeda, J. D. Goodpaster, J. C. Peters, T. F. Miller III, ACS Catal., 6, 6114-6123 (2016).

Cobalt Catalysts

Accurate and systematically improvable density functional theory embedding for correlated wavefunctions

J. D. Goodpaster, T. A. Barnes, F. R. Manby, and T. F. Miller III, J. Chem. Phys., 140, 18A507 (2014)

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