A benchmark for non-covalent interactions in organometallic crystals

Area of Science:

• Solid-state chemistry
• Computational chemistry
• Materials science

Background:

• Organometallic complexes are vital in catalysis, materials science, and pharmaceuticals.
• Intermolecular interactions in solid-state transition metal complexes influence thermodynamics and bioavailability.
• Non-covalent forces like hydrogen bonding stabilize these crystal structures.

Purpose of the Study:

• To compare experimental sublimation heats with periodic DFT calculations for organometallic complexes.
• To establish a benchmark dataset (XTMC43) for evaluating computational methods.
• To assess the accuracy of density functional theory (DFT) functionals in predicting intermolecular interactions.

Main Methods:

• Manual curation of 43 experimental heats of sublimation for the XTMC43 set.
• Periodic Density Functional Theory (DFT) calculations using GGA or mGGA functionals.
• Employing atom-centered Gaussian-type basis functions for calculations.

Main Results:

• Achieved agreement within 9% between experimental and calculated sublimation heats.
• Demonstrated the efficacy of GGA and mGGA functionals for predicting intermolecular interactions.
• Highlighted the importance of data consistency, calibration, and reproducibility.

Conclusions:

• The XTMC43 set serves as a valuable benchmark for computational method development.
• Accurate prediction of intermolecular interactions is feasible with appropriate DFT methods.
• This work supports advancements in crystal engineering and the design of organometallic materials.