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Theoretical Investigation on Local Structure Distortion of V4+-Doped DUT-5(Al) via EPR Parameter Calculation
Yun-Chao Zhu1, Chang-Chun Ding1, De-Chuan Sun1
1School of Science, Key Laboratory of High Performance Scientific Computation, Xihua University, Chengdu, China.
Abstract:
To clarify the correlation between the V4+ doping and the structure of DUT-5(Al), this study establishes a theoretical calculation model for the electron paramagnetic resonance (EPR) parameters of V4+ with a 3d1 electron configuration in orthorhombically compressed octahedrons. After verifying the rationality of the model by fitting with experimental data, the local structural distortion of [VO6] clusters, the regulation mechanism of electronic states, and the essence of EPR components (lp, np, BL, and Blp) were systematically analyzed. The findings reveal that, due to the Jahn-Teller distortion, the [VO6] units adopt an orthorhombically distorted octahedral structure, quantified by an axial compression parameter ρ ranging from 5.6% to 6.4%, and in-plane bond-length variation rate τ spanning 6.0% to 6.8%. The theoretical method adopted in this study can clarify the doping mechanism of transition metal ions in metal-organic frameworks (MOFs), provide theoretical support for interpreting the EPR phenomena of V4+-doped DUT-5(Al), and offer guidance for the rational design and performance optimization of transition metal-doped MOF materials.
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