Density functional theory calculations of copper-doped rutile crystals: Local structural, electronic, optical, and electron paramagnetic resonance properties
| Autor: | Li Yan, Xiao-Yu Li, Xing-Yuan Yu, Shao-Yi Wu, Gao-Qiang Shen, Zhang-Ting Wei |
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| Rok vydání: | 2021 |
| Předmět: |
Chemistry
Band gap General Chemistry Molecular physics law.invention Condensed Matter::Materials Science Molecular geometry Absorption band Rutile law Condensed Matter::Superconductivity Density of states Condensed Matter::Strongly Correlated Electrons General Materials Science Density functional theory Electron paramagnetic resonance Mulliken population analysis |
| Zdroj: | Magnetic resonance in chemistry : MRCREFERENCES. 60(1) |
| ISSN: | 1097-458X |
| Popis: | The local structural, electronic, optical, and electron paramagnetic resonance (EPR) properties are uniformly studied for Cu2+ -doped rutile (TiO2 ) crystals by using the density functional theory (DFT) calculations. The local cation-oxygen bond lengths and planar bond angle, band gap, Mulliken charge and overlapping population, density of state (DOS), and UV-Vis absorption spectra are calculated for pure and copper-doped rutile. The smaller overlapping population of Cu-O bonds in the doped system than Ti-O bonds in pure rutile reflects weaker orbital admixtures or covalency of the former. Compared with pure rutile, Cu2+ doping leads to significant redshift of the UV-Vis absorption band and the narrow impurity band in visible and near-infrared regions arising from the Cu2+ d-d transitions and narrowing of the band gap by about 0.636 eV, possibly suggesting enhancement of visible light activity. The Cu dopant induces a spin magnetic moment of 0.74 μB for the doped rutile. The calculated UV-Vis absorption spectra and spin Hamiltonian parameters for copper-doped rutile show reasonable agreement with the experimental data and some improvement related to the previous perturbation formula calculations. Present systematic studies would be helpful to understand the mechanisms of the enhancement in the optical and magnetic properties of this material with transition-metal (especially Cu2+ ) dopants. |
| Databáze: | OpenAIRE |
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