Downshift of <i>d</i>-states and the decomposition of silver halides

Geng Yanlei; Li Jianfu; Zhang Zhaobin; Lv Yang; Lu Mengxin; Zhu Mengyuan; Liu Yong; Yuan Jianan; Hu Qingyang; Wang Xiaoli

doi:10.1063/5.0216221

Volume 9 Issue 6

Nov. 2024

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Article Navigation > Matter and Radiation at Extremes > 2024 > 9(6): 067804

Geng Yanlei, Li Jianfu, Zhang Zhaobin, Lv Yang, Lu Mengxin, Zhu Mengyuan, Liu Yong, Yuan Jianan, Hu Qingyang, Wang Xiaoli. Downshift of d-states and the decomposition of silver halides[J]. Matter and Radiation at Extremes, 2024, 9(6): 067804. doi: 10.1063/5.0216221

Citation:

Geng Yanlei, Li Jianfu, Zhang Zhaobin, Lv Yang, Lu Mengxin, Zhu Mengyuan, Liu Yong, Yuan Jianan, Hu Qingyang, Wang Xiaoli. Downshift of d-states and the decomposition of silver halides[J]. Matter and Radiation at Extremes, 2024, 9(6): 067804. doi: 10.1063/5.0216221

Citation:

Geng Yanlei, Li Jianfu, Zhang Zhaobin, Lv Yang, Lu Mengxin, Zhu Mengyuan, Liu Yong, Yuan Jianan, Hu Qingyang, Wang Xiaoli. Downshift of d-states and the decomposition of silver halides[J]. Matter and Radiation at Extremes, 2024, 9(6): 067804. doi: 10.1063/5.0216221

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Downshift of d-states and the decomposition of silver halides

doi: 10.1063/5.0216221

1.
School of Physics and Electronic Information, Yantai University, Yantai 264005, China
2.
Center for High Pressure Science and Technology Advanced Research, Beijing 100193, China

More Information

Corresponding author: a)Authors to whom correspondence should be addressed: jianfuli@ytu.edu.cn and xlwang@ytu.edu.cn
Received Date: 2024-04-28
Accepted Date: 2024-08-25

Available Online: 2024-11-01

Publish Date: 2024-11-01

Abstract

Abstract

The ionicity of ionic solids is typically characterized by the electronegativity of the constituent ions. Electronegativity measures the ability of electron transfer between atoms and is commonly considered under ambient conditions. However, external stresses profoundly change the ionicity, and compressed ionic compounds may behave differently. Here, we focus on silver halides, with constituent ions from one of the most electropositive metals and some of the most electronegative nonmetals. Using first-principles calculations, we find that the strengths of the ionic bonds in these compounds change greatly under pressure owing to downshifting of the Ag 4d-orbital. The center of this orbital is lowered to fill the antibonding state below the Fermi level, leading to chemical decomposition. Our results suggest that under pressure, the orbital energies and correspondingly the electronegativities still tune the ionicity and control the electron transfer, ionicity, and reactivity of both the metal and the nonmetal elements. However, the effects of orbital energies start to become dominant under pressure, causing substantial changes to the chemistry of ionic compounds and leading to an unusual phenomenon in which elements with substantial electronegativity differences, such as Ag and Br, do not necessarily form ionic compounds, but remain in their elemental forms.

Conflict of Interest
The authors have no conflicts to disclose.
Author Contributions
Yanlei Geng: Data curation (equal); Formal analysis (equal); Investigation (equal); Methodology (equal); Software (equal); Validation (equal); Visualization (equal); Writing – original draft (equal). Jianfu Li: Formal analysis (equal); Funding acquisition (equal); Project administration (equal); Validation (equal); Writing – review & editing (equal). Zhaobin Zhang: Formal analysis (equal); Investigation (equal); Validation (equal). Yang Lv: Formal analysis (equal); Investigation (equal); Validation (equal). Mengxin Lu: Formal analysis (equal); Investigation (equal); Validation (equal). Mengyuan Zhu: Formal analysis (equal); Investigation (equal); Validation (equal). Yong Liu: Formal analysis (equal); Investigation (equal); Validation (equal). Jianan Yuan: Formal analysis (equal); Investigation (equal); Validation (equal). Qingyang Hu: Formal analysis (equal); Validation (equal); Writing – review & editing (equal). Xiaoli Wang: Data curation (equal); Formal analysis (equal); Funding acquisition (equal); Methodology (equal); Project administration (equal); Supervision (equal); Validation (equal); Writing – review & editing (equal).
The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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