Electronic structure and chemical bonding in the OTi-N2 complexes: a systematic ab initio and DFT study

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• The TiO + N2 reaction yields OTi-N2 complexes.
• Accurate theoretical models are needed to understand their properties.

Purpose of the Study:

• To theoretically investigate two OTi-N2 complexes.
• To evaluate the performance of various computational methods.

Main Methods:

• Ab initio and density functional theory (DFT) calculations.
• Coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) as benchmark.
• Assessment of pure, hybrid, double-hybrid, and long-range corrected DFT functionals.
• Topological and localized orbital analyses for bonding.

Main Results:

• Twenty-three DFT functionals were tested against CCSD(T) reference data.
• Only TPSS0, LC-TPSS, and B2PLYP accurately reproduced the benchmark results.
• The B2PLYP double-hybrid functional demonstrated the highest accuracy.

Conclusions:

• B2PLYP is a highly promising DFT functional for studying OTi-N2 complexes.
• The bonding nature within the complexes was elucidated using advanced analytical techniques.