Bond-Resolved Analysis of Oxygen Vacancy Migration in 3d Transition-Metal Oxides

Understanding migration barriers of ions is essential for controlling ionic transport in functional materials [1,2]. However, identifying migration pathways and assessing migration barriers through density functional theory (DFT) calculations remain computationally demanding, especially for large-scale screening [3,4]. In this study, we perform a bond-based analysis, connecting quantum-mechanical bonding descriptors with empirical models, for oxygen vacancy (V_O) migration in 3d transition-metal dioxides (TMO₂). We attempt to integrate crystal orbital Hamilton population (COHP) method [5] and bond valence theory (BVT) [6]. The summed integrated COHP defines an effective covalent bond strength, complemented by the ionic contribution represented by the Madelung energy. We find that their averaged value reproduces migration barriers across TMO₂ compounds. Our results support that the unified bond-based analysis effectively captures both covalent and ionic effects, demonstrating the potential of a computationally efficient approach to assess migration properties in oxides.

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