Catalysts by Design: The Power of Theory

Hammes‐Schiffer, Sharon

doi:10.1021/acs.accounts.6b00555

Cited by 68 publications

(62 citation statements)

References 31 publications

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“…Unfortunately, we were unable to extract the total number of gradient calls for the SC-AFIR calculations as we did not have access to the corresponding source code. The total number of unique saddle points detected by SC-AFIR was rather small (7).…”

Section: Computational/statistical Detailsmentioning

confidence: 94%

Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

et al. 2018

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Ketohydroperoxides are important in liquid-phase autoxidation and in gas-phase partial oxidation and pre-ignition chemistry, but because of their low concentration, instability, and various analytical chemistry limitations, it has been challenging to experimentally determine their reactivity, and only a few pathways are known. In the present work, 75 elementary-step unimolecular reactions of the simplest γ-ketohydroperoxide, 3-hydroperoxypropanal, were discovered by a combination of density functional theory with several automated transition-state search algorithms: the Berny algorithm coupled with the freezing string method, single- and double-ended growing string methods, the heuristic KinBot algorithm, and the single-component artificial force induced reaction method (SC-AFIR). The present joint approach significantly outperforms previous manual and automated transition-state searches - 68 of the reactions of γ-ketohydroperoxide discovered here were previously unknown and completely unexpected. All of the methods found the lowest-energy transition state, which corresponds to the first step of the Korcek mechanism, but each algorithm except for SC-AFIR detected several reactions not found by any of the other methods. We show that the low-barrier chemical reactions involve promising new chemistry that may be relevant in atmospheric and combustion systems. Our study highlights the complexity of chemical space exploration and the advantage of combined application of several approaches. Overall, the present work demonstrates both the power and the weaknesses of existing fully automated approaches for reaction discovery which suggest possible directions for further method development and assessment in order to enable reliable discovery of all important reactions of any specified reactant(s).

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Section: Computational/statistical Detailsmentioning

confidence: 94%

Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

et al. 2018

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“…Based on these data, an extended version of WingPhos was designed ( L6 ) that is predicted to provide enhanced stereoselectivity and catalytic activity. Although the age of the purely computational catalyst design is not yet upon us, this work represents a key step toward this goal by providing tools for the automated quantum mechanical prediction of stereoselectivities of reactions with well‐established mechanisms but variability regarding the stereodetermining step.…”

Section: Methodsmentioning

confidence: 99%

Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium‐Catalyzed Asymmetric Hydrogenation

Guan

Wheeler

2017

Angew Chem Int Ed

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A computational toolkit (AARON: An automated reaction optimizer for new catalysts) is described that automates the density functional theory (DFT) based screening of chiral ligands for transition-metal-catalyzed reactions with well-defined reaction mechanisms but multiple stereocontrolling transition states. This is demonstrated for the Rh-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, for which a new C -symmetric phosphorus ligand is designed.

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“…Significant approaches here include advances in semiconductors, nanotechnology, synthetic biology and genetic engineering, photochemistry and photophysics, and device engineering. [26] Synthetic biology in a hybrid inorganic/biological approach aims to create a renewable chemical synthesis platform utilizing accelerated metabolic pathways. [27] One such system involves electrolysis water splitting powered by a solar cell and facilitated by catalytic, cobalt/ phosphate electrodes for oxygen evolution and NiMoZn electrodes for hydrogen evolution.…”

Section: Artificial Photosynthesis As the Ultimate Renewable Energy Smentioning

confidence: 99%

Global Artificial Photosynthesis and Renewable Energy Storage and Policy for the Sustainocene

Faunce

2018

Advanced Sustainable Systems

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Among developing strategies for renewable energy conversion and storage, artificial photosynthesis (AP) has many long‐term advantages over currently favored strategies such as small‐ and large‐scale lithium‐ion batteries. Such advantages may not be clearly revealed by recent methods of AP including hybrid nanotechnology–synthetic biology systems. This paper critiques some of these recent developments in the context of the long‐term goal of integrating AP (conducted without enslaving biological life) into every road and building on the Earth's surface. It considers the advantages and disadvantages of this as a long‐term energy storage solution and reflects on how such disadvantages may be overcome.

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Catalysts by Design: The Power of Theory

Cited by 68 publications

References 31 publications

Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium‐Catalyzed Asymmetric Hydrogenation

Global Artificial Photosynthesis and Renewable Energy Storage and Policy for the Sustainocene

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