The Keith group applies and develops computational chemistry to study and discover solutions to problems at the interface of engineering and basic science. They are currently focused on modeling chemical reaction mechanisms and the atomic scale of materials to help develop renewable energy and sustainability technologies.
The group uses quantum chemistry-based multiscale modeling to predict and study the atomic scale of materials and chemical reactions. With electronic structure and atomistic methods, they can investigate fundamental reaction steps at different time- and length-scales that would otherwise be difficult or impossible to investigate with experiment.
Notably, their studies are entirely carried out in silico (on a computer) and almost entirely free from artificial biases that are present when using experimental inputs. Whether doing so alone or in collaboration with experimentalists, the group provides deep perspective on the atomic-scale of catalytic environments to understand how they work and how to further improve them.
The 'ground-up' multiscale modeling approach uses appropriate levels of quantum chemistry (QC) theory (typically on up to ca. 200 atoms) to model reaction energies, barrier heights, pKas, and standard redox potentials. Using data obtained from QC theory, they can also develop analytic reactive forcefields, which are capable of modeling reaction dynamics on systems on the order of 100,000 atoms. Reactive forcefield data in turn can be used to generate rate constant libraries for kinetic Monte Carlo (kMC) simulations to model larger time-scale and length-scale phenomena such a nanoparticle/material growth and ripening.
- "Water Oxidation on Pure and Doped Hematite (0001) Surfaces: Prediction of Co and Ni as Effective Dopants for Electrocatalysis," Peilin Liao, John A. Keith, and Emily A. Carter, J. Am. Chem. Soc. 134, 13296 (2012)
- "The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations," John A. Keith, Patrick M. Henry, Angew. Chem. Int. Ed. 48, 9038 (2009)
- "Theoretical Studies of Potential-Dependent and Competing Mechanisms of the Electrocatalytic Oxygen Reduction Reaction on Pt(111)," John A. Keith, Timo Jacob, Angew. Chem. Int. Ed. 49, 9521 (2010)
- "Theoretical Investigations of the Oxygen Reduction Reaction on Pt(111)," John A. Keith, Gregory Jerkiewicz, Timo Jacob, ChemPhysChem 11, 2779 (2010)
- "Theoretical insights into pyridinium-based photoelectrocatalytic reduction of CO2," John A Keith, Emily A. Carter. Journal of the American Chemical Society 134, no. 18 (2012): 7580-7583.
- "Mechanism of Isobutylene Polymerization: Quantum Chemical Insight into AlCl3/H2O‑Catalyzed Reactions," Minh Nguyen Vo, Yasemin Basdogan, Bridget S. Derksen, Nico Proust, G. Adam Cox, Cliff Kowall, John A. Keith, and J. Karl Johnson, ACS Catal., 8, 8006 (2018)
- "Oligomer Hydrate Crystallization Improves Carbon Nanotube Memory," Michael T. Chido, Peter Koronaios, Karthikeyan Saravanan, Alexander P. Adams, Steven J. Geib, Qiang Zhu, Hari B Sunkara, Sachin S. Velankar, Robert M. Enick, John A. Keith, and Alexander Star, Chemistry of Materials (2018).
- "Thermodynamic Hydricities of Biomimetic Organic Hydride Donors," Stefan Ilic, Usha Pandey Kadel, Yasemin Basdogan, John A. Keith, and Ksenija D. Glusac, J. Am. Chem. Soc. (2018)
- "Quantum chemistry benchmarking of binding and selectivity for lanthanide extractants," Minh Nguyen Vo, Vyacheslav S. Bryantsev, J. Karl Johnson, John A. Keith, International Journal of Quantum Chemistry (2017)
- "A sobering assessment of small-molecule force field methods for low energy conformer predictions," IIana Y. Kanal, John A. Keith, Geoffrey R. Hutchison, International Journal of Quantum Chemistry (2017)
- "Alchemical Predictions for Computational Catalysis: Potential and Limitations," Karthikeyan Saravanan, John R. Kitchin, O. Anatole von Lilienfeld, and John A. Keith, J. Phys. Chem. Lett., 8 , 5002 (2017)
- "Quantum Chemical Analyses of BH4- and BH3OH- Hydride Transfers to CO2 in Aqueous Solution with Potentials of Mean Force," Mitchell C. Groenenboom, John Andrew Keith, ChemPhysChem 18, 1 (2017)