Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study
The defect structures and electronic properties of orthorhombic elongated (O E ) and tetragonal compressed (T C ) Rh 2+ centers in LiD are theoretically studied using Density Functional Theory (DFT) with the periodic CP2K program. The calculations demonstrate obvious differences in defect structure...
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crwiley:10.1002/pssb.201800026 2024-06-02T08:12:48+00:00 Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study Wu, Li‐Na Wu, Shao‐Yi Liu, Xu‐Sheng Zhong, Si‐Ying Zhang, Fu National Natural Science Foundation of China 2018 http://dx.doi.org/10.1002/pssb.201800026 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpssb.201800026 https://onlinelibrary.wiley.com/doi/pdf/10.1002/pssb.201800026 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor physica status solidi (b) volume 255, issue 7 ISSN 0370-1972 1521-3951 journal-article 2018 crwiley https://doi.org/10.1002/pssb.201800026 2024-05-03T10:56:10Z The defect structures and electronic properties of orthorhombic elongated (O E ) and tetragonal compressed (T C ) Rh 2+ centers in LiD are theoretically studied using Density Functional Theory (DFT) with the periodic CP2K program. The calculations demonstrate obvious differences in defect structure between the two centers. O E center with one next nearest neighbor (nnn) cation vacancy (V Li ) in [100] axis shows the Jahn‐Teller elongation of about 0.076 Å along [001] axis, whereas T C center with one nnn V Li in [001] axis exhibits a compression of about 0.049 Å along this direction. The ligand between the central Rh 2+ and the V Li is found to move away from the V Li by about 0.038 or 0.035 Å for O E or T C center. The larger magnitude of the overlap population (≈ −0.5907 or −0.5494 e) of the RhD bonds in O E or T C center than that (≈0.2373 e) of the host LiD bonds in pure LiD indicates much stronger covalency of the former. The simulated UV–Vis and electron paramagnetic resonance (EPR) spectra with the embedded cluster model in ORCA code are consistent with the experimental data. The present results are discussed and compared with those of the previous perturbation calculations. Article in Journal/Newspaper Orca Wiley Online Library physica status solidi (b) 255 7 |
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English |
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The defect structures and electronic properties of orthorhombic elongated (O E ) and tetragonal compressed (T C ) Rh 2+ centers in LiD are theoretically studied using Density Functional Theory (DFT) with the periodic CP2K program. The calculations demonstrate obvious differences in defect structure between the two centers. O E center with one next nearest neighbor (nnn) cation vacancy (V Li ) in [100] axis shows the Jahn‐Teller elongation of about 0.076 Å along [001] axis, whereas T C center with one nnn V Li in [001] axis exhibits a compression of about 0.049 Å along this direction. The ligand between the central Rh 2+ and the V Li is found to move away from the V Li by about 0.038 or 0.035 Å for O E or T C center. The larger magnitude of the overlap population (≈ −0.5907 or −0.5494 e) of the RhD bonds in O E or T C center than that (≈0.2373 e) of the host LiD bonds in pure LiD indicates much stronger covalency of the former. The simulated UV–Vis and electron paramagnetic resonance (EPR) spectra with the embedded cluster model in ORCA code are consistent with the experimental data. The present results are discussed and compared with those of the previous perturbation calculations. |
author2 |
National Natural Science Foundation of China |
format |
Article in Journal/Newspaper |
author |
Wu, Li‐Na Wu, Shao‐Yi Liu, Xu‐Sheng Zhong, Si‐Ying Zhang, Fu |
spellingShingle |
Wu, Li‐Na Wu, Shao‐Yi Liu, Xu‐Sheng Zhong, Si‐Ying Zhang, Fu Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study |
author_facet |
Wu, Li‐Na Wu, Shao‐Yi Liu, Xu‐Sheng Zhong, Si‐Ying Zhang, Fu |
author_sort |
Wu, Li‐Na |
title |
Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study |
title_short |
Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study |
title_full |
Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study |
title_fullStr |
Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study |
title_full_unstemmed |
Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study |
title_sort |
defect structures, electronic properties, uv–vis, and epr parameters for rh 2+ centers in lid: a dft study |
publisher |
Wiley |
publishDate |
2018 |
url |
http://dx.doi.org/10.1002/pssb.201800026 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpssb.201800026 https://onlinelibrary.wiley.com/doi/pdf/10.1002/pssb.201800026 |
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Orca |
genre_facet |
Orca |
op_source |
physica status solidi (b) volume 255, issue 7 ISSN 0370-1972 1521-3951 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/pssb.201800026 |
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physica status solidi (b) |
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255 |
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7 |
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