High Accuracy Barrier Heights, Enthalpies, and Rate Coefficients for Chemical Reactions

This Zenodo repository contains the data presented in Spiekermann, K. A.; Pattanaik, L.; Green, W. H.* High Accuracy Barrier Heights, Enthalpies, and Rate Coefficients for Chemical Reactions, Sci. Data 9, 417, (2022). We recommend people refer to this dataset as RDB7 i.e. a diverse reaction database whose transition states contain up to 7 heavy atoms.

Atom-mapped SMILES, barrier heights, reaction enthalpies, and Reaction Mechanism Generator (RMG) reaction family for each reaction are listed in the comma-separated values files b97d3.csv, wb97xd3.csv, ccsdtf12_dz.csv, and ccsdtf12_tz.csv. Q-Chem output files from the reoptimized products are provided for 16,302 reactions at B97-D3/def2-mSVP and for 11,926 reactions at ωB97X-D3/def2-TZVP level of theory. For convenience, these also include the original log files for the reactant, transition state, and non-reoptimized products from Grambow et al. (10.5281/zenodo.3715478) since they were used to calculate barrier heights, enthalpies, and rate constants in this work. The numbering of reaction indices matches that from the originally published dataset to facilitate easy comparison. MOLPRO output files from the single point calculations are provided for 11,926 reactions at the CCSD(T)-F12/cc-pVDZ-F12 level of theory as well as for the 15 validation reactions run at CCSD(T)-F12/cc-pVTZ-F12. The raw log files for all calculations are stored in b97d3.tar.gz, wb97xd3.tar.gz, ccsdtf12_dz.tar.gz, and ccsdtf12_tz.tar.gz. Each archive contains a separate folder for each reaction, which contains log files for the reactant, transition state, and product/s. The Q-Chem log files contain the output from a geometry optimization and harmonic vibrational analysis while the MOLPRO log files contain output from an energy calculation. Transition state theory rate constants, fitted Arrhenius parameters, and average percentage error between the calculated and fitted rate constants can be found for the rigid reactions in ccsdtf12_dz_rigid.csv. The list of 50 temperatures (K) used during Arrhenius fitting is provided in arkane_temperatures.csv, and the raw Arkane outputs are provided in ccsdtf12_dz_rigid.tar.gz.

The improvement from fitting bond additivity corrections at B97-D3/def2-mSVP, ωB97X-D3/def2-TZVP, CCSD(T)-F12/cc-pVDZ-F12//ωB97X-D3/def2-TZVP, and CCSD(T)-F12/cc-pVTZ-F12//ωB97X-D3/def2-TZVP is shown in b97d3_def2msvp_BAC.csv, wb97xd3_def2tzvp_BAC.csv, ccsdtf12_ccpvdzf12__wb97xd3_def2tzvp_BAC.csv, and ccsdtf12_ccpvtzf12__wb97xd3_def2tzvp_BAC.csv respectively. The files contain the experimental and calculated enthalpies for the reference species from the RMG-database used for fitting. The correction values are publicly stored on the RMG-database GitHub on the AEC_BAC branch, though they are also provided in fitted_corrections.pkl for convenience. Further validation of the BACs at the double zeta level was done by comparing to experimental values from the Pedley set since over half of these molecules were not in the RMG-database training set used for fitting. The comparison is shown in ccsdtf12_dz_vs_Pedley_experimental.csv.