DFT calculations of the defect structures, electronic structures, and EPR parameters for three Rh 2+ centers in AgCl

• Published in: Magnetic Resonance in Chemistry
• Main Authors: Wu, Li‐Na, Wu, Shao‐Yi, Zhong, Si‐Ying, Zhang, Li‐Juan, Tan, Qin‐Qin
• Other Authors: National Natural Science Foundation of China
• Format: Article in Journal/Newspaper
• Language: English
• Published: Wiley 2017
• Subjects: Orca
• Online Access: http://dx.doi.org/10.1002/mrc.4685; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fmrc.4685; https://onlinelibrary.wiley.com/doi/full/10.1002/mrc.4685

The local structures for various Rh 2+ centers in AgCl are theoretically studied using density functional theory (DFT) with periodic CP2K program. Through geometry optimizing, the stable ground states with minimal energies and electronic structures are obtained for the tetragonally elongated (T E ), orthorhombically elongated (O E ), and tetragonally compressed (T C ) centers, and the corresponding g and hyperfine coupling tensors are calculated in ORCA level. The calculations reveal obvious Jahn–Teller elongation distortions of about 0.109 and 0.110 Å along [001] axis for T E and O E centers without and with 1 next nearest neighbor (nnn) cation vacancy V Ag in [100] axis, respectively. Whereas T C center with 1 nnn V Ag along [001] axis exhibits moderate axial compression of about 0.066 Å due to the Jahn–Teller effect. For O E and T C centers with 1 nnn V Ag , the ligand intervening in the central Rh 2+ and the V Ag is found to displace away from the V Ag by about 0.028 and 0.024 Å, respectively. The present results are discussed and compared with those of the previous calculations based on the perturbation formulas by using the improved ligand field theory.