Department of Chemistry, University of Pittsburgh
Ph.D., Computational Organic Chemistry, University of California, 2010

Reactivity and Selectivity Rules in Organic and Organometallic Reactions
We are developing computational models to quantitatively describe the origins of reactivity and selectivity in organocatalytic and transition metal-catalyzed reactions. We perform quantum mechanical calculations to explore the reaction mechanism, followed by thorough analysis on various stereoelectronic effects to predict how changes of the catalyst structure, substituents, and solvent affect rate and selectivity. We use quantitative energy decomposition methods to dissect the key interactions in the transition state and provide chemically meaningful interpretation to the computed reactivity and selectivity. We apply these computational studies to a broad range of organic and organometallic reactions, such as C–H and C–C bond activations, coupling reactions, olefin metathesis, and polymerization reactions. 

Catalyst Screening and Prediction
We are developing a multi-scale computational screening protocol which could efficiently rank the catalysts based on ligand-substrate interaction energies in the transition state. 

Applications of Computational Chemistry in Understanding Organic Chemistry
We are collaborating with experimental groups at Pitt and many other institutions to solve problems in organic chemistry using computational methods and programs. Our goal is to establish the most effective strategy to use modern computational methods and hardware to help address the grand challenges in synthetic chemistry. 


Most Cited Publications
  1. "Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions." Gavin O Jones, Peng Liu, KN Houk, Stephen L Buchwald. Journal of the American Chemical Society.
  2. "Suzuki− Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies." Kyle W Quasdorf, Aurora Antoft-Finch, Peng Liu, Amanda L Silberstein, Anna Komaromi, Tom Blackburn, Stephen D Ramgren, KN Houk, Victor Snieckus, Neil K Garg. Journal of the American Chemical Society.
  3. "Conversion of amides to esters by the nickel-catalysed activation of amide CN bonds." Liana Hie, Noah F Fine Nathel, Tejas K Shah, Emma L Baker, Xin Hong, Yun-Fang Yang, Peng Liu, KN Houk, Neil K Garg. Nature.
  4. "Palladium-Catalyzed Meta-Selective C–H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity." Yun-Fang Yang, Gui-Juan Cheng, Peng Liu, Dasheng Leow, Tian-Yu Sun, Ping Chen, Xinhao Zhang, Jin-Quan Yu, Yun-Dong Wu, KN Houk. Journal of the American Chemical Society.
  5. "Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies." Xiangcheng Pan, Cheng Fang, Marco Fantin, Nikhil Malhotra, Woong Young So, Linda A Peteanu, Abdirisak A Isse, Armando Gennaro, Peng Liu, Krzysztof Matyjaszewski. Journal of the American Chemical Society.
Recent Publications
  1. "Ruthenium-Catalyzed Reductive Cleavage of Unstrained Aryl─ Aryl Bonds: Reaction Development and Mechanistic Study." Jun Zhu, Peng-hao Chen, Gang Lu, Peng Liu, Guangbin Dong. Journal of the American Chemical Society.
  2. "The Thermal Rearrangement of an NHC‐Ligated 3‐Benzoborepin to an NHC‐Boranorcaradiene." Masaki Shimoi, Ilia Kevlishvili, Takashi Watanabe, Steven J Geib, Katsuhiro Maeda, Dennis P Curran, Peng Liu, Tsuyoshi Taniguchi. Angewandte Chemie.
  3. "Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP." Jessica K Su, Zexin Jin, Rui Zhang, Gang Lu, Peng Liu, Yan Xia. Angewandte Chemie.
  4. "An enzymatic platform for the asymmetric amination of primary, secondary and tertiary C (sp 3)–H bonds." Yang Yang, Inha Cho, Xiaotian Qi, Peng Liu, Frances H Arnold. Nature chemistry.
  5. "Diastereo-and Enantioselective CuH-Catalyzed Hydroamination of Strained Trisubstituted Alkenes." Sheng Feng, Hua Hao, Peng Liu, Stephen L Buchwald. ChemRxiv.
Department of Chemical and Petroleum Engineering, University of Pittsburgh
Ph.D., Chemistry, California Institute of Technology, 2007

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 energiesbarrier heightspKas, 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.

Most Cited Publications
  1. "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)
  2. "The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations," John A. Keith, Patrick M. Henry, Angew. Chem. Int. Ed. 48, 9038 (2009)
  3. "Theoretical Investigations of the Oxygen Reduction Reaction on Pt(111)," John A. Keith, Gregory Jerkiewicz, Timo Jacob, ChemPhysChem 11, 2779 (2010)
  4. "Elucidation of the selectivity of proton-dependent electrocatalytic CO2 reduction by fac-Re (bpy)(CO) 3CI," JA Keith, KA Grice, CP Kubiak, and EA Carter.  Journal of the American Chemical Society 135.42 (2013)
  5. "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)
Recent Publications
  1. "Machine Learning Guided Approach for Studying Solvation Environments,"  Y Basdogan, MC Groenenboom, E Henderson, S De, S Rempe, and J KeithChemRxiv (2019)
  2. "Free Standing Nanoporous Palladium Alloys as CO Poisoning Tolerant Electrocatalysts for the Electrochemical Reduction of CO2 to Formate," S Chatterjee, CD Griego, J Hart, Y Li, M Taheri, J Keith, and J Snyder.  ACS Catalysis 9.6 (2019)
  3. "Benchmarking Computational Alchemy for Carbide, Nitride, and Oxide Catalysts." Griego, Charles D., Karthikeyan Saravanan, and John A. Keith. Advanced Theory and Simulations (2018): 1800142.
  4. "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)
  5. "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).
Department of Chemical and Petroleum Engineering, University of Pittsburgh
Ph.D., Chemical Engineering, Cornell University, 1992

The Johnson group tackles fundamental problems over a wide range of subject areas using state-of-the-art atomistic modeling methods. Current projects include CO2 capture through the following methods:

  • Selective adsorption in metal organic frameworks (MOFs).
  • Catalytic nanoparticles on amorphous supports.
  • Multiscale modeling proton-exchange membrane (PEM) based fuel cells.  
  • Hydrogen storage in metal hydrides.
  • Absorption into ionic liquids, including ionic liquids that react chemically with CO2.
  • Physical absorption of CO2 into liquid sorbents.
  • Chemical capture involving carbamate forming amines.
  • Solid-state reactions involving carbonates and bicarbonates.

Tools we use in our studies include Kohn-Sham density functional theory, first principles quantum mechanics methods, classical equilibrium and non-equilibrium molecular dynamics, and Monte Carlo simulation techniques.

Most Cited Publications
  1. "The Lennard-Jones equation of state revisited," J. Karl Johnson, John A. Zollweg & Keith E. Gubbins, Molecular Physics 78, 591 (1993)
  2. "Microporous Metal Organic Materials:  Promising Candidates as Sorbents for Hydrogen Storage," Long Pan, Michelle B. Sander, Xiaoying Huang, Jing Li, Milton Smith, Edward Bittner, Bradley Bockrath, and J. Karl JohnsonJ. Am. Chem. Soc. 126, 1308 (2004)
  3. "Rapid Transport of Gases in Carbon Nanotubes," Anastasios I. Skoulidas, David M. Ackerman, J. Karl Johnson, and David S. Sholl, Phys. Rev. Lett. 89, 185901 (2002)
  4. "Molecular simulation of hydrogen adsorption in single-walled carbon nanotubes and idealized carbon slit pores," Qinyu Wang and J. Karl JohnsonJ. Chem. Phys. 110, 577 (1999)
  5. "Adsorption of Gases in Metal Organic Materials:  Comparison of Simulations and Experiments," Giovanni Garberoglio, Anastasios I. Skoulidas, and J. Karl JohnsonJ. Phys. Chem. B 109, 13094 (2005)
Recent Publications
  1. "Toward Understanding the Kinetics of CO2 Capture on Sodium Carbonate."  Tianyi Cai, J Karl Johnson, Ye Wu, Xiaoping Chen.  ACS applied materials and interfaces (2019)
  2. "Graphamine: Amine-Functionalized Graphane for Intrinsic Anhydrous Proton Conduction." A Bagusetty, J Livingston, and JK JohnsonJournal of Phys. Chem. C 123.3. (2018)
  3. "Energy Efficient Formaldehyde Synthesis by Direct Hydrogenation of Carbon Monoxide in Functionalized Metal-Organic Frameworks."  Lin Li, Sen Zhang, Johathan P Ruffley, and J Karl JohnsonACS Sustainable Chemistry and Engineering 7.2. (2018)
  4. "TiH2 as a Dynamic Additive for Improving the De/Rehydrogenation Properties of MgH2: A Combined Experimental and Theoretical Mechanistic Investigation," Ashish Bhatnagar, J. Karl Johnson, M. A. Shaz, and O. N. Srivastava, J. Phys. Chem. C 122, 21248 (2018).
  5. "The effect of topology in Lewis pair functionalized metal organic frameworks on CO2 adsorption and hydrogenation,"Jingyun Ye, Lin Li and J. Karl Johnson, Catal. Sci. Technol.(2018)

Quantum-Engineered Catalysts that Turn Excess Atmospheric CO2 into Liquid Fuel

  • By Aude Marjolin
  • 8 December 2015

PQI faculty Karl Johnson and his team recently identified the two main factors for determining the optimal catalyst for turning atmospheric CO2 into liquid fuel. The results of the study, which appeared in the journal ACS Catalysis, will streamline the search for an inexpensive yet highly effective new catalyst.

Imagine a power plant that takes the excess carbon dioxide (CO2) put in the atmosphere by burning fossil fuels and converts it back into fuel. Now imagine that power plant uses only a little water and the energy in sunlight to operate. The power plant wouldn't burn fossil fuels and would actually reduce the amount of CO2 in the atmosphere during the manufacturing process. For millions of years, actual plants have been using water, sunlight, and CO2 to create sugars that allow them to grow. Scientists around the globe are now adopting their energy-producing behavior.


John Keith Awarded ACS Petroleum Research Fund to Study CO2 Recycling Catalysts

  • By Aude Marjolin
  • 24 July 2015

To further his research in renewable energy catalysts, the American Chemical Society Petroleum Research Fund recently awarded a Doctoral New Investigator Award to PQI faculty John A. Keith. The two-year, $110,000 grant, "Unraveling Heterocycle-Promoted Hydride Transfer Mechanisms for Energetically Efficient Fuel and Petrochemical Production" will enable Dr. Keith to study design principles for renewable energy catalysts that efficiently convert CO2 into fuels and chemicals. 

Quantum Mechanics Identifies Link Between CO2 Recycling Catalysts and Bimolecular Enzymes

  • By Aude Marjolin
  • 22 January 2015

Researchers at PQI have identified a promising design principle for renewable energy catalysts. Utilizing advanced computational modeling, researchers found that chemicals commonly found in laboratories may play a similar role as biological catalysts that nature uses for efficient energy storage.

The article, "Thermodynamic Descriptors for Molecules That Catalyze Efficient CO  Electroreductions" published in the journal ACS Catalysis, was authored by PQI faculty John A. Keith, PhD, and Aude Marjolin, PhD, a postdoctoral fellow.