Thousands of reactants and transition states for competing E2 and S2 reactions

• Published in: Machine learning: science and technology Vol. 1; no. 4
• Main Authors: Guido Falk von Rudorff, Heinen, Stefan N, Bragato, Marco, O Anatole von Lilienfeld
• Format: Journal Article
• Language: English
• Published: Bristol IOP Publishing 01.12.2020
• Subjects: Chemical compounds; First principles; Halogens; Machine learning; Nitrogen dioxide; Nucleophiles; Quantum chemistry
• ISSN: 2632-2153
• DOI: 10.1088/2632-2153/aba822

Reaction barriers are a crucial ingredient for first principles based computational retro-synthesis efforts as well as for comprehensive reactivity assessments throughout chemical compound space. While extensive databases of experimental results exist, modern quantum machine learning applications require atomistic details which can only be obtained from quantum chemistry protocols. For competing E2 and S\(_\mathrm{N}\)2 reaction channels we report 4,466 transition state and 143,200 reactant complex geometries and energies at MP2/6-311G(d) and single point DF-LCCSD/cc-pVTZ level of theory, respectively, covering the chemical compound space spanned by the substituents NO2, CN, CH3, and NH2 and early halogens (F, Cl, Br) and hydrogen as nucleophiles and early halogens as leaving groups. Reactants are chosen such that the activation energy of the competing E2 and S\(_\mathrm{N}\)2 reactions are of comparable magnitude. The correct concerted motion for each of the one-step reactions has been validated for all transition states. We demonstrate how quantum machine learning models can support data set extension, and discuss the distribution of key internal coordinates of the transition states.