The BOS-TMC Dataset: DFT Properties of 159k Experimentally Characterized Transition Metal Complexes Spanning Multiple Charge and Spin States

TL;DR

The BOS-TMC dataset provides extensive DFT properties for 159,000 experimentally characterized transition metal complexes across multiple charge and spin states, supporting machine learning and benchmarking.

Contribution

This work introduces a large, diverse dataset of transition metal complexes with multiple spin states and properties, curated with an iterative charge assignment process, and reports over 2.9 million properties.

Findings

Dataset is larger and more diverse than prior TMC datasets.

Properties are computed with PBE0/def2-TZVP and include multiple electronic and atomic features.

Sensitivity analysis shows variation in properties depending on exchange-correlation functional.

Abstract

We present the Boston Open-Shell Transition Metal Complex (BOS-TMC) dataset, a set of density functional theory (DFT) properties for 159k experimentally characterized mononuclear transition metal complexes (TMCs) in multiple spin states with a range of formal charges derived from the Cambridge Structural Database (CSD). To curate this set, we carried out an iterative procedure to confidently assign overall TMC charge. From this information, we then obtained properties in up to three spin states, i.e., low-, intermediate-, and high-spin for 3d metals and low- and intermediate-spin for 4d and 5d metals, depending on compatibility with the metal electron configuration, for a total of 343.8k TMC/spin combinations. At odds with prior sets, we preserved experimental heavy-atom coordinates in these structures during optimization. We report all properties using PBE0/def2-TZVP single-point energies on these structures. We introduce a scheme for computing metal-spin-dependent atomization energies, which we report for each TMC. Alongside electronic energies, we report up to seven additional properties including: HOMO, LUMO, HOMO-LUMO gap, atomic partial charges, dipole moments, atomization energies, and spin-splitting energies for a total of over 2.9M TMC-associated properties. For a representative subset of over 10k complexes chosen based on size, we evaluate the sensitivity of computed properties to exchange-correlation (xc) functional choice from a set of twelve xcs spanning rungs of "Jacob's ladder", highlighting hotspots of TMC space that have the greatest uncertainty. In comparison to prior transition-metal datasets, BOS-TMC is both larger and more diverse in terms of charge and spin configurations and, as a result, more diverse in its range of properties. This dataset is expected to provide a high-fidelity foundation for machine-learning model development, DFT benchmarking, and exploration.