Reactants, Products, and Transition States of Elementary Chemical Reactions Based on Quantum Chemistry

Grambow, Colin A.; Pattanaik, Lagnajit; Green, William

doi:10.26434/chemrxiv.11400240

Cited by 9 publications

(12 citation statements)

References 31 publications

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“…We also justify our choice of level of theory by noting that similar levels of theory have previously been used to generate datasets used to study reactivity. In particular, Grambow et al 70 recently used the ωB97X-D3 density functional 71 (which is closely related to ωB97X-V and differs primarily in the choice of dispersion correction) and the def2-TZVP basis set (which is part of the same family as def2-TZVPPD but contains no diffuse functions and fewer polarization functions) to create a dataset 6/27 of over 12,000 organic reactions (including optimized reactants, products, and transition states) in vacuum. The solution-phase charged and radical organometallic chemistry involved in SEI formation is more complex than the gas-phase organic reactions considered by Grambow et al, necessitating both the inclusion of an implicit solvent model and the use of a larger basis set including diffuse functions.…”

Section: Level Of Theorymentioning

confidence: 99%

“…31), lithium ethylene dicarbonate (LEDC) and related derivatives(32)(33)(34)(35), lithium butylene dicarbonate (LBDC) and related derivatives(36)(37)(38)(39)(40)(41)(42)(43), lithium ethylene monocarbonate (LEMC) and related derivatives(44)(45)(46)(47)(48)(49)(50)(51)(52)(53)(54)(55)(56), ethanol and related derivatives (57-58), ethylene glycol (EG) and related derivatives (59-66), 1,4-butanediol and related derivatives(67)(68)(69), other molecules related to LiEC decomposition(70)(71)(72)(73), and other molecules related to PF 6 decomposition (74-83).…”

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confidence: 99%

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Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

Spotte-Smith

Blau²,

Xie³

et al. 2021

Preprint

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Lithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte(LIBE) dataset reported here aims to provide accurate first-principles data to improve the understanding of SEI species and associated reactions. The dataset was generated by fragmenting a set of principal molecules, including solvents, salts, and SEI products, and then selectively recombining a subset of the fragments. All candidate molecules were analyzed at theωB97X-V/def2-TZVPPD/SMD level of theory at various charges and spin multiplicities. In total, LIBE contains structural,thermodynamic, and vibrational information on over 17,000 unique species. In addition to studies of reactivity in LIBs, this dataset may prove useful for machine learning of molecular and reaction properties.

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Section: Level Of Theorymentioning

confidence: 99%

mentioning

confidence: 99%

Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

Spotte-Smith

Blau²,

Xie³

et al. 2021

Preprint

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“…Q-Chem output files, extracted SMILES, activation energies, and enthalpies of formation are available for 16,365 B97-D3/def2-mSVP reactions and for 11,961 ωB97X-D3/def2-TZVP reactions 40 . The raw log files are stored in two compressed archive files, b97d3.tar.gz and wb97xd3.tar.gz for B97-D3/def2-mSVP and ωB97X-D3/def2-TZVP data, respectively.…”

Section: Data Recordsmentioning

confidence: 99%

Reactants, Products, and Transition States of Elementary Chemical Reactions Based on Quantum Chemistry

Grambow¹,

Pattanaik²,

Green³

2020

Preprint

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Reaction times, activation energies, branching ratios, yields, and many other quantitative attributes are important for precise organic syntheses and generating detailed reaction mechanisms. Often, it would be useful to be able to classify proposed reactions as fast or slow. However, quantitative chemical reaction data, especially for atom-mapped reactions, are difficult to find in existing databases. Therefore, we used automated potential energy surface exploration to generate 12,000 organic reactions involving H, C, N, and O atoms calculated at the ωB97X-D3/def2-TZVP quantum chemistry level. We report the results of geometry optimizations and frequency calculations for reactants, products, and transition states of all reactions. Additionally, we extracted atom-mapped reaction SMILES, activation energies, and enthalpies of reaction. We believe that this data will accelerate progress in automated methods for organic synthesis and reaction mechanism generation—for example, by enabling the development of novel machine learning models for quantitative reaction prediction.

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“…[33][34][35][36] Other benchmark sets either focus on specific types of reactions, or they contain only a handful of data points, or they are not evaluated using a reference level of enough quality to allow benchmarking commonly used quantum mechanical methods. 28,31,32,[37][38][39][40][41][42][43] The current necessity of a benchmark set for enzymatically catalyzed reactions has been emphasized several times recently. 31,32,44 Local correlation methods, particularly DLPNO-CCSD(T), have become very popular recently due to a favorable combination of relatively high accuracy and modest computational cost.…”

Section: Introductionmentioning

confidence: 99%

BH9, a New Comprehensive Benchmark Dataset for Barrier Heights and Reaction Energies: Assessment of Density Functional Approximations and Basis Set Incompleteness Potentials

Prasad

Pei

Edelmann

et al. 2021

Preprint

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The calculation of accurate reaction energies and barrier heights is essential in computational studies of reaction mechanisms and thermochemistry. In order to assess methods regarding their ability to predict these two properties, high-quality benchmark sets are required that comprise a reasonably large and diverse set of organic reactions. Due to the time-consuming nature of both locating transition states and computing accurate reference energies for reactions involving large molecules, previous benchmark sets have been limited in scope, the number of reactions considered, and the size of the reactant and product molecules. Recent advances in coupled-cluster theory, in particular local correlation methods like DLPNO-CCSD(T), now allow the calculation of reaction energies and barrier heights for relatively large systems. In this work, we present a comprehensive, and diverse benchmark set of barrier heights and reaction energies based on DLPNO-CCSD(T)/CBS, called BH9. BH9 comprises 449 chemical reactions belonging to nine types common in organic chemistry and biochemistry. We examine the accuracy of DLPNO-CCSD(T) vis-a-vis canonical CCSD(T) for a subset of BH9 and conclude that, although there is a penalty in using the DLPNO approximation, the reference data are accurate enough to serve as benchmark for density-functional theory (DFT) methods. We then present two applications of the BH9 set. First, we examine the performance of several density functional approximations commonly used in thermochemical and mechanistic studies. Second, we assess our basis set incompleteness potentials regarding their ability to mitigate basis set incompleteness error. The number of data points, the diversity of the reactions considered, and the relatively large size of the reactant molecules make BH9 the most comprehensive thermochemical benchmark set to date, and a useful tool for the development and assessment of computational methods.

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Reactants, Products, and Transition States of Elementary Chemical Reactions Based on Quantum Chemistry

Cited by 9 publications

References 31 publications

Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

Reactants, Products, and Transition States of Elementary Chemical Reactions Based on Quantum Chemistry

BH9, a New Comprehensive Benchmark Dataset for Barrier Heights and Reaction Energies: Assessment of Density Functional Approximations and Basis Set Incompleteness Potentials

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