High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions

Abstract

<jats:title>Abstract</jats:title><jats:p>Quantitative chemical reaction data, including activation energies and reaction rates, are crucial for developing detailed kinetic mechanisms and accurately predicting reaction outcomes. However, such data are often difficult to find, and high-quality datasets are especially rare. Here, we use CCSD(T)-F12a/cc-pVDZ-F12//<jats:italic>ω</jats:italic>B97X-D3/def2-TZVP to obtain high-quality single point calculations for nearly 22,000 unique stable species and transition states. We report the results from these quantum chemistry calculations and extract the barrier heights and reaction enthalpies to create a kinetics dataset of nearly 12,000 gas-phase reactions. These reactions involve H, C, N, and O, contain up to seven heavy atoms, and have cleaned atom-mapped SMILES. Our higher-accuracy coupled-cluster barrier heights differ significantly (RMSE of ∼5 kcal mol<jats:sup>−1</jats:sup>) relative to those calculated at <jats:italic>ω</jats:italic>B97X-D3/def2-TZVP. We also report accurate transition state theory rate coefficients <jats:inline-formula><jats:alternatives><jats:tex-math>$${k}_{\infty }(T)$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msub> <mml:mrow> <mml:mi>k</mml:mi> </mml:mrow> <mml:mrow> <mml:mi>∞</mml:mi> </mml:mrow> </mml:msub> <mml:mrow> <mml:mo>(</mml:mo> <mml:mrow> <mml:mi>T</mml:mi> </mml:mrow> <mml:mo>)</mml:mo> </mml:mrow> </mml:math></jats:alternatives></jats:inline-formula> between 300 K and 2000 K and the corresponding Arrhenius parameters for a subset of rigid reactions. We believe this data will accelerate development of automated and reliable methods for quantitative reaction prediction.</jats:p>