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Strain and ligand effect on the electronic structure of Ni-Fe and Ni-Cu alloys: Exploring charge redistribution from x-ray spectroscopies and the charge compensation model |
| Zeel Patel1, Lu Yao1, Zhiqiang Wang1, Yun Mui Yiu1, Tsun-Kong Sham1,†, Sarah Purdy2, Jianfeng Zhu2, and Sammynaiken Ramaswami2 |
1 Department of Chemistry, Western University, London ON, Canada N6A 5B7;
2 Saskatchewan Structural Science Centre, University of Saskatchewan, Saskatoon SK Canada S7N 5C9 |
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Abstract Nickel-based bimetallic alloys are considered thermally and structurally stable, while also possessing desirable catalytic and magnetic functionalities and being highly abundant and affordable. The electronic structure of such alloys is of particular interest from the perspective of atomic size mismatch and elemental crystal structure compatibility. In this study, we utilize x-ray techniques, including x-ray diffraction (XRD), x-ray absorption spectroscopy (XAS), and x-ray photoelectron spectroscopy (XPS), to understand the strain and ligand effects on charge redistribution upon alloying. We investigate the elemental crystal structures for incompatible alloys of Ni (fcc) and Fe (bcc), and the compatible crystal structure of Ni (fcc) and Cu (fcc) for comparison. Emphasis is placed on interpreting the metal 2p XPS binding energy shift in binary alloys, where one element is diluted into the other, based on the framework of strain and ligand effects and the charge compensation model of Watson et al. Of interest are the different ``compressibilities'' of the 4s and 3d wavefunctions within the Wigner-Seitz volume, $V_{\rm WS}$, and the volume-strain effect resulting in intra-atomic 4s-3d rehybridizations within the alloy, as well as the chemical intuition of charge transfer based on the ligand effect (electronegativity). These considerations provide perspective on ``internal pressure'' due to the strain effect and help in understanding the x-ray data and their correlation with the electronic structures and properties of bimetallic alloy systems.
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Received: 03 November 2025
Revised: 25 December 2025
Accepted manuscript online:
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PACS:
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61.05.C-
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(X-ray diffraction and scattering)
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61.05.cj
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(X-ray absorption spectroscopy: EXAFS, NEXAFS, XANES, etc.)
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73.61At
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| Fund: Research at the University of Western Ontario is supported by NSERC (DG and RTI), CRC, CFI, and OIT, as well as the Canada Research Chair program (TKS). XPS was conducted at Surface Science Western, and the technical assistance of Jeff Henderson is greatly appreciated. The Saskatchewan Structural Sciences Centre (SSSC) is acknowledged for providing facilities to conduct this research. Funding from the Canada Foundation for Innovation, the Natural Sciences and Engineering Research Council of Canada, and the University of Saskatchewan supports research at the SSSC. |
Corresponding Authors:
Tsun-Kong Sham
E-mail: tsham@uwo.ca
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Cite this article:
Zeel Patel, Lu Yao, Zhiqiang Wang, Yun Mui Yiu, Tsun-Kong Sham, Sarah Purdy, Jianfeng Zhu, and Sammynaiken Ramaswami Strain and ligand effect on the electronic structure of Ni-Fe and Ni-Cu alloys: Exploring charge redistribution from x-ray spectroscopies and the charge compensation model 2026 Chin. Phys. B 35 056101
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