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| Format: | Preprint |
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2025
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| Online Access: | https://arxiv.org/abs/2504.02054 |
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| _version_ | 1866915346877775872 |
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| author | Lei, Ming Abate, Iwnetim I. |
| author_facet | Lei, Ming Abate, Iwnetim I. |
| contents | Polarons are quasiparticles that arise from the coupling of electrons or holes with ionic vibrations in polarizable materials. Typically, they are either localized at a single atomic site or delocalized over multiple sites. However, after the desodiation of Na$_{2}$Mn$_{3}$O$_{7}$, we identify a rare split-hole polaron, where a single hole is shared between two adjacent oxygen atoms rather than fully localized or delocalized. We present a density functional theory (DFT) study on the migration and transport properties of these oxygen hole polarons in NaMn$_{3}$O$_{7}$ and Na$_{1.5}$Mn$_{3}$O$_{7}$. Our calculations reveal that the split polaron configuration near a sodium vacancy is the ground state, while the localized polaron acts as the transition state. Migration occurs via a stepwise charge transfer mechanism along the $b$-axis, where the split-hole polaron transitions through a localized hole state. This transport behavior closely resembles the Grotthuss mechanism, which describes proton transport in H$_{2}$O. We compute the polaron mobility as $μ$ = 1.37 $\times$ 10$^{-5}$ cm$^2$/(V$\cdot$s) with an energy barrier of 242 meV. Using the Mulliken-Hush theory, we determine the electronic coupling parameter $V_{AB}$ = 0.87 eV. A similar migration mechanism is observed in Na$_{1.5}$Mn$_{3}$O$_{7}$, where the split polaron remains more stable than in the localized state. This study provides the first theoretical investigation of split-hole polaron migration, offering new insights into the charge transport of exotic polaronic species in materials with implications for a wide range of functional materials including battery cathodes, thermoelectrics, photocatalysts, and next-generation optoelectronic devices. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2504_02054 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Grotthuss-type oxygen hole polaron transport in desodiated Na$_{2}$Mn$_3$O$_7$ Lei, Ming Abate, Iwnetim I. Materials Science Polarons are quasiparticles that arise from the coupling of electrons or holes with ionic vibrations in polarizable materials. Typically, they are either localized at a single atomic site or delocalized over multiple sites. However, after the desodiation of Na$_{2}$Mn$_{3}$O$_{7}$, we identify a rare split-hole polaron, where a single hole is shared between two adjacent oxygen atoms rather than fully localized or delocalized. We present a density functional theory (DFT) study on the migration and transport properties of these oxygen hole polarons in NaMn$_{3}$O$_{7}$ and Na$_{1.5}$Mn$_{3}$O$_{7}$. Our calculations reveal that the split polaron configuration near a sodium vacancy is the ground state, while the localized polaron acts as the transition state. Migration occurs via a stepwise charge transfer mechanism along the $b$-axis, where the split-hole polaron transitions through a localized hole state. This transport behavior closely resembles the Grotthuss mechanism, which describes proton transport in H$_{2}$O. We compute the polaron mobility as $μ$ = 1.37 $\times$ 10$^{-5}$ cm$^2$/(V$\cdot$s) with an energy barrier of 242 meV. Using the Mulliken-Hush theory, we determine the electronic coupling parameter $V_{AB}$ = 0.87 eV. A similar migration mechanism is observed in Na$_{1.5}$Mn$_{3}$O$_{7}$, where the split polaron remains more stable than in the localized state. This study provides the first theoretical investigation of split-hole polaron migration, offering new insights into the charge transport of exotic polaronic species in materials with implications for a wide range of functional materials including battery cathodes, thermoelectrics, photocatalysts, and next-generation optoelectronic devices. |
| title | Grotthuss-type oxygen hole polaron transport in desodiated Na$_{2}$Mn$_3$O$_7$ |
| topic | Materials Science |
| url | https://arxiv.org/abs/2504.02054 |