Ab initio modeling of complex amorphous transition-metal-based ceramics

Area of Science:

• Materials Science
• Computational Chemistry
• Solid State Physics

Background:

• Amorphous transition metal (TM) nitrides and oxides are crucial for applications like high-temperature machining and optical filters.
• Understanding their electronic structure and bonding is challenging due to d electrons in the valence band.

Purpose of the Study:

• To investigate the structure and electronic structure of ZrSiN using ab initio calculations.
• To develop and validate a computational methodology for analyzing bonding in TM-based systems, particularly those with d electrons.

Main Methods:

• Ab initio calculations were performed to study ZrSiN.
• A modified Wannier function center-based algorithm was developed to address limitations with d electrons.
• The impact of calculation length on convergence was assessed.

Main Results:

• The traditional Wannier function algorithm failed for TM systems with d electrons.
• A modified algorithm successfully analyzed bonding structures in these materials.
• Valence p states of TM atoms were observed in ZrSiN, NbO(x), and WAuO, influencing bonding character.

Conclusions:

• The developed computational methodology is effective for analyzing bonding in TM-based ceramics.
• The presence and importance of TM valence p states in bonding were highlighted.
• This work provides insights into both physical phenomena and computational approaches for TM ceramics.