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

doi:10.1088/1674-1056/ae3691

中国物理B ›› 2026, Vol. 35 ›› Issue (5): 56101-056101.doi: 10.1088/1674-1056/ae3691

所属专题： SPECIAL TOPIC — John Tse: Pioneer in high-pressure materials science

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 Sham^1,†, 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

收稿日期:2025-11-03 修回日期:2025-12-25 接受日期:2026-01-12 出版日期:2026-04-24 发布日期:2026-01-12
通讯作者: Tsun-Kong Sham E-mail:tsham@uwo.ca
基金资助:
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.

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 Sham^1,†, 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

Received:2025-11-03 Revised:2025-12-25 Accepted:2026-01-12 Online:2026-04-24 Published:2026-01-12
Contact: Tsun-Kong Sham E-mail:tsham@uwo.ca
Supported by:
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.

摘要/Abstract

摘要： 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.

关键词: bimetallic alloys, strain and ligand effect, renormalized atom, charge compensation model, x-ray spectroscopy, M?ssbauer spectroscopy

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.

Key words: bimetallic alloys, strain and ligand effect, renormalized atom, charge compensation model, x-ray spectroscopy, M?ssbauer spectroscopy

中图分类号: (X-ray diffraction and scattering)

61.05.C-

61.05.cj (X-ray absorption spectroscopy: EXAFS, NEXAFS, XANES, etc.) 73.61.At (Metal and metallic alloys)

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[J]. 中国物理B, 2026, 35(5): 56101-056101.

参考文献

[2] Zhang Y, Zuo T T, Tang Z, Gao M C, Dahmen K A, Liaw P K and Lu Z P 2014 Prog. Mater. Sci. 61 1
[3] Nakamura M, Lee S, Kim J, Park H, Tanaka K and Suzuki Y 2025 ACS Nano 5 196
[4] Chen J, Finfrock Y Z, Wang Z and Sham T K 2021 Sci. Rep. 11 13698
[5] Mankins W L and Lamb S 1990 ASM Handb. 2 428
[6] Meloni E, Martino M and Palma V A 2020 Catalysts 10 352
[7] Wang W, Su C, Wu Y, Ran R and Shao Z 2013 Chem. Rev. 113 8104
[8] Tomishige K, Li D, Tamura M and Nakagawa Y 2017 Catal. Sci. Technol. 7 3952
[9] Shok J and Kawi S 2014 ACS Catal. 4 289
[10] Sahoo A and Medicherla V R R 2021 Mater. Today 43 2242
[11] Waeckerlé T 2010 IEEE Trans. Magn. 46 326
[12] Kittel C 1996 Introduction to Solid State Physics 7th edn (New York: Wiley)
[13] Wigner E and Seitz F 1933 Phys. Rev. 43 804
[14] Denton A R and Ashcroft N W 1991 Phys. Rev. A 43 3161
[15] Gelatt Jr. C D, Ehrenreich H and Watson R E 1977 Phys. Rev. B 15 1613
[16] Watson R E and Perlman M L 1974 Photoelectron Spectrometry, in Structure and Bonding 24 p. 83 (Berlin: Springer)
[17] Watson R E, Perlman M L and Herbst J F 1976 Phys. Rev. B 13 2358
[18] Hodges L, Watson R E and Ehrenreich H 1972 Phys. Rev. B 5 3953
[19] Watson R E, Hudis J and Perlman M L 1971 Phys. Rev. B 4 4139
[20] Pauling L 1930 The Nature of the Chemical Bond (Ithaca, NY: Cornell University Press)
[21] Sham T K, Perlman M L and Watson R E 1979 Phys. Rev. B 19 539
[22] Sham T K, Yiu Y M, KuhnMand Tan K H 1990 Phys. Rev. B 41 11881
[23] Kuhn M, Bzowski A, Sham T K, Rodriguez J A and Hrbek J 1996 The Solid Films 283 209
[24] Sham T K, Perlman M L and Watson R E 1979 Phys. Rev. B 20 3552
[25] Wang D, Cui X, Xiao Q, Hu Y, Wang Z and Sham T K 2008 AIP Adv. 8 065210
[26] Hüfner S, Wertheim G K, Cohen R L and Wernick J H 1972 Phys. Rev. Lett. 28 488
[27] Kistner O C and Sunyar A W 1960 Phys. Rev. Lett. 4 412
[28] Lehlooh A F and Mahmood S H 2002 Hyperfine Interact. 139 387
[29] Kuhn M, Bzowski A and Sham T K 1994 Hyperfine Interact. 94 2267
[30] Watson R E and Perlman M L 1980 Phys. Scr. 21 527
[31] Ohtsu N, Oku M, Shishido T and Wagatsuma K 2007 Appl. Surf. Sci. 253 8713
[32] Skriver H L and Rosengaard N M 1992 Phys. Rev. B 46 7157
[33] Vegard L 1921 Z. Phys. 5 17
[34] Stern E A, Sayers D E and Lytle F W 1975 Phys. Rev. B 11 48
[35] Coulthard I and Sham T K 1996 Phys. Rev. Lett. 77 4824
[36] Sham T K and Carr R 1985 J. Chem. Phys. 83 5914
[37] Hsieh H H, Tsai M S, Lin H J, Chen C T, Wu S C and Hsieh H C 1998 Phys. Rev. B 57 15204
[38] Massalski T B, Okamoto H, Subramanian P R and Kacprzak L 1990 Binary Alloys Phase Diagrams, 2nd edn (Metals Park, OH: ASM International)
[39] Fairley N, Barlow A J, Carrick A M R, Roberts M E, Smith J and Wilson R 2021 Appl. Surf. Sci. Adv. 5 100112
[40] ATENA: XAS Data Processing
[41] Kohn W and Sham L J 1965 Phys. Rev. 140 A1133
[42] Blaha P, Schwarz K, Sorantin P and Trickey S B 1990 Comput. Phys. Commun. 59 399
[43] Yiu Y M 2017 Applications of Chalcogenides: S, Se, and Te (Switzerland: Springer)
[44] Materials Project
[45] Perdew J P and Wang Y 1992 Phys. Rev. B 45 13244
[46] Perdew J P, Burke K and Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[47] Doniach S and Sunjic M 1970 J. Phys. C Solid State Phys. 3 285
[48] Chen J, Li X, Wang Y, Zhang H, Liu Z and Wu Y 2020 J. Phys. Chem. C 124 2313
[49] Valderruten J F, Pérez Alcázar G A and Grenèche J M 2008 J. Phys. Condens. Matter 20 485204
[50] de Groot F M F, Kotani A, van Aken P A and Stavitski E 2024 Nat. Rev. Methods Primers 4 45

[1]	Chenglong Zhang(张成龙), Haochen Gu(谷昊琛), Yu Dai(戴羽), Ke Fang(方可), Yufeng Dong(董玉峰), Peng Zhou(周鹏), and Yingjun Li(李英骏). Diagnosis of electron temperature of copper foil plasmas produced at the Shenguang-II facility[J]. 中国物理B, 2025, 34(7): 75202-075202.
[2]	Supeng Chen(陈苏鹏), Yingli Li(李英丽), Yande Li(李彦德), Keqiang Li(李克强), Peirong Li(李培荣), Jianwei Meng(孟建伟), Zilong Zhao(赵子龙), Yuanyuan Pan(潘圆圆), Qinghao Li(李庆浩), and Pengfei Yu(于鹏飞). Oxygen activation-triggered thermal instability in Li(Ni_0.8Co_0.1Mn_0.1)O₂ cathode[J]. 中国物理B, 2025, 34(10): 108201-108201.
[3]	Rui Huang(黄瑞), Tian Lan(兰天), Chong Li(李冲), Jing Li(李景), and Zhiyong Wang(王智勇). Fabrication of GaAs/SiO₂/Si and GaAs/Si heterointerfaces by surface-activated chemical bonding at room temperature[J]. 中国物理B, 2021, 30(7): 76802-076802.
[4]	杨万里, 乔瑞敏. Soft x-ray spectroscopy for probing electronic and chemical states of battery materials[J]. 中国物理B, 2016, 25(1): 17104-017104.
[5]	叶凡, 李正宏, 秦义, 蒋树庆, 薛飞彪, 杨建伦, 徐荣昆, 金永杰. Spatially-resolved spectroscopic diagnosing of aluminum wire array Z-pinch plasmas on QiangGuang-I facility[J]. 中国物理B, 2010, 19(7): 75204-075204.
[6]	温福昇, 乔亮, 周栋, 左文亮, 伊海波, 李发伸. Influence of shape anisotropy on microwave complex permeability in carbonyl iron flakes/epoxy resin composites[J]. 中国物理B, 2008, 17(6): 2263-2267.
[7]	寇志起, 邸乃力, 鲁毅, 马骁, 李庆安, 成昭华. Local structural distortion and magnetotransport properties of Nd_0.5Pb_0.5-xSr_x (Mn, Fe)O₃[J]. 中国物理B, 2005, 14(2): 311-316.
[8]	罗志, 邸乃力, 寇志起, 成昭华, 刘立君, 陈立泉, 黄学杰. M?ssbauer study and magnetic properties of electrochemical material LiFePO₄[J]. 中国物理B, 2004, 13(12): 2158-2161.
[9]	戴耀东, 王林, 杨亚新, 何云, 黄红波, 夏元复. A M?ssbauer study of the magnetic coupling in iron phosphorous trisulfides[J]. 中国物理B, 2004, 13(10): 1652-1656.

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

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

RichHTML

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 9

Metrics

本文评价

推荐阅读 0