Metal-organic frameworks properties from hybrid density functional approximations.

Area of Science:

• Computational materials science
• Solid-state chemistry
• Quantum chemistry

Background:

• Metal-Organic Frameworks (MOFs) offer versatile applications due to their unique hybrid structure.
• Accurate ab initio modeling of large MOFs (e.g., MIL-100, MIL-101) with thousands of atoms presents significant computational challenges.

Purpose of the Study:

• To introduce and validate a class of composite electronic structure methods (sol-3c) for efficient ab initio calculations on large MOFs.
• To demonstrate the feasibility and accuracy of sol-3c methods for predicting diverse MOF properties.

Main Methods:

• Utilized hybrid functionals (PBEsol0, HSEsol) combined with double-zeta basis sets.
• Incorporated semi-classical corrections (D3, gCP) for dispersive interactions and basis set superposition error.
• Applied the developed sol-3c methodologies to model large MOFs, including MIL-100 and MIL-101.

Main Results:

• The sol-3c methods provide a cost-effective approach to achieve hybrid functional accuracy for MOF calculations.
• Successfully performed calculations on very large MOFs (over 2500 atoms) with reasonable computational resources.
• Accurately predicted structural, vibrational, electronic, and adsorption properties of common MOFs.

Conclusions:

• The sol-3c composite methods offer a robust and efficient tool for the ab initio modeling of complex, large-scale MOFs.
• These methods are suitable for routine in silico screening of MOFs, extending beyond basic structural characterization.
• Facilitates computational exploration of MOFs for advanced material design and application discovery.