Kinetics dataset

[craabreu]

This PR collects the QuantumPioneer Kinetics Dataset: gas-phase rate coefficients and Arrhenius parameters for hydrogen-atom-transfer (HAT) reactions, along with ZPE-corrected forward barriers and reaction enthalpies.

Contents

• quantumpioneer_kinetics_dataset.csv — Curated, unique HAT reactions between hydrogen donors (D–H) and peroxyl radicals (ROO•; predominantly hydroperoxyl HOO• and hydroxymethyl-peroxyl HOCH2OO•). It includes:
  • Gas-phase bimolecular rate coefficients computed at 298 K using conventional TST with 1D Eckart tunneling.
  • Rate coefficients computed over 300–2000 K, then fit to two Arrhenius regimes: 300–1000 K (A_low, Ea_low) and 1000–2000 K (A_high, Ea_high).
  • ZPE-corrected reaction enthalpies (Hrxn) and forward barriers (barrier) derived from the underlying QM energies.

Source and Processing

The dataset combines:

1. Rate data from TS calculations (DFT-optimized, DLPNO single-point rates): rate coefficient at 298 K and Arrhenius parameters in low- and high-temperature ranges.
2. Thermochemical data (ZPE-scaled DLPNO/DFT values): forward barrier and forward reaction enthalpy.

QM protocol:

ωB97X-D/def2-SVP geometries and DLPNO-CCSD(T)-F12d/def2-TZVP single points, with kinetic parameters derived via Arkane/TST + Eckart tunneling (see the QuantumPioneer manuscript for details).

Processing steps:

• Reaction SMILES are built from reactant and product SMILES (r1, r2, p1, p2) as r1.r2>>p1.p2.
• SMILES are canonicalized (RDKit, atom maps removed) for consistent representation.
• Rows with duplicate rxn_smi are dropped (keep=False), so only reactions with a unique SMILES are retained.