Correlation Between Fermi-Energy, Chemical Shifts, and Surface Plasmon Resonance in Cu and Zn Compounds under X-ray Illumination

Ram, Tika; Kumar, Ajay; Kumar, Dinesh; Juneja, Poonam; Rathore, Sanjeev; Krishan, Hari; Kumar, Narinder

doi:10.22075/ppam.2025.39045.1170

اداره چاپ و انتشارات دانشگاه سمنان

تعداد نشریات	22
تعداد شماره‌ها	705
تعداد مقالات	10,146
تعداد مشاهده مقاله	71,454,834
تعداد دریافت فایل اصل مقاله	63,176,402

	Correlation Between Fermi-Energy, Chemical Shifts, and Surface Plasmon Resonance in Cu and Zn Compounds under X-ray Illumination
Progress in Physics of Applied Materials
دوره 6، شماره 2 - شماره پیاپی 11، مهر 2026، صفحه 99-110 اصل مقاله (579.26 K)
نوع مقاله: Original Article
شناسه دیجیتال (DOI): 10.22075/ppam.2025.39045.1170
نویسندگان
Tika Ram¹؛ Ajay Kumar^* ²؛ Dinesh Kumar³؛ Poonam Juneja⁴؛ Sanjeev Rathore⁵؛ Hari Krishan⁶؛ Narinder Kumar¹
¹Department of Physics, Uttaranchal Institute of Technology, Uttaranchal University, Dehradun-248007, Uttarakhand, India
²Department of Chemistry, School of Applied and Life Sciences, Uttaranchal Institute of Technology, Uttaranchal University, Dehradun-248007, Uttarakhand, India
³Uttar Pradesh State of Higher Education Council, Lucknow, Uttar Pradesh, India
⁴Department of Physics, Maitreyi College, University of Delhi, Delhi, India
⁵Department of Physics, Government Degree College, Badaun, -243601, Uttar Pradesh, India
⁶Department of Chemistry, Michigan Diagnostic LLC, 2611 Parmenter Blvd, Royal Oak, MI, USA 48073.
تاریخ دریافت: 25 شهریور 1404، تاریخ بازنگری: 09 آبان 1404، تاریخ پذیرش: 13 آبان 1404
چکیده
This study represents an integrated theoretical framework that correlates copper (Cu) and zinc (Zn) compounds with variation in Fermi energy, chemical shifts, and surface plasmon resonance (SPR) under X-ray illumination. A simplified but conscientious model was developed to determine chemical shifts in X-ray K-absorption spectra based on Fermi energy differences between metals and their compound states. The model incorporates electron concentration, plasmon energy, and effective charge to predict more clearly the sign as well as the amount of chemical shift without depending on empirical adaptation. Experimental X-ray absorption data closely match the expected chemical shifts (2.7-6.0 eV for Cu compounds and 2.4-4.7 eV for Zn compounds), confirming the model's reliability. A correlation between Fermi energy and effective charge confirms that electron redistribution of compounds governs spectral edge shifts under X-ray illumination. Furthermore, the conceptual link between Fermi-level modulation and SPR behavior illustrates that variations in conduction electron density are influenced by X-ray illumination. This correlation reveals a consistent theoretical explanation for photo-induced plasmonic phenomena in Cu, Zn, and their compounds based materials. Overall, the suggested model enhances perception of the Fermi energy dependence of chemical shifts and extends its applicability to plasmonic materials. The current study offers a frontier analysis tool that will be used for the electronic and optical properties of transition-metal compounds.
کلیدواژه‌ها
Chemical shift؛ Fermi energy؛ Surface plasmon resonance؛ Plasmon energy؛ X-ray illumination

مراجع
[1] Agarwal, B.K. and Verma, L.P., 1970. A rule for chemical shifts of X-ray absorption edges. Journal of Physics C: Solid State Physics, 3(3), p.535. [2] Pan, J., Gao, B., Guo, K., Gao, Y., Xu, X. and Yue, Q., 2022. Insights into selective adsorption mechanism of copper and zinc ions onto biogas residue-based adsorbent: Theoretical calculation and electronegativity difference. Science of the Total Environment, 805, p.150413. [3] Singh, V.P., Singh, S., Singh, D.P., Singh, P., Tiwari, K., Mishra, M. and Butcher, R.J., 2013. Synthesis, spectral and single crystal X-ray diffraction studies on Co (II), Ni (II), Cu (II) and Zn (II) complexes with o-amino acetophenone benzoyl hydrazone. Polyhedron, 56, pp.71-81. [4] Kawata, S. and Maeda, K., 1973. Effects of chemical combination on the X-ray LIII absorption limits of Mo, Rh, Pd, Ag and Cd. Journal of Physics F: Metal Physics, 3(1), p.167. [5] Salem, S.I., Chang, C.N., Lee, P.L. and Severson, V., 1978. Energy shift of the K-absorption edge of Mn and Fe compounds. Journal of Physics C: Solid State Physics, 11(19), p.4085. [6] Joseph, D., Basu, S., Jha, S.N. and Bhattacharyya, D., 2012. Chemical shifts of K X-ray absorption edges on copper in different compounds by X-ray absorption spectroscopy (XAS) with synchrotron radiation. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 274, pp.126–128. [7] Joseph, D. and Patra, N., 2017. Chemical shift at the X-ray K-absorption edge of Zn in some Zn compounds. Madridge Journal of Analytical Sciences and Instrumentation, 2(1), pp.25–27. [8] Rudolph, J. and Jacob, C.R., 2018. Revisiting the dependence of Cu K-edge X-ray absorption spectra on oxidation state and coordination environment. Inorganic Chemistry, 57(17), pp.10591–10607. [9] Batail, P., 2004. Introduction: molecular metals. Chemical Reviews, 104(11), pp.4887–4890. [10] Pendharkar, A.V. and Mande, C., 1973. Fine structure of the rhenium LIII absorption discontinuity. Physica, 66(1), pp.204–210. [11] Tzeng, C.T., Lo, W.S., Yuh, J.Y., Chu, R.Y. and Tsuei, K.D., 2000. Photoemission, near-edge X-ray absorption spectroscopy, and low-energy electron-diffraction study of C₆₀ on Au (111) surfaces. Physical Review B, 61(3), p.2263. [12] Solomon, E.I., Hedman, B., Hodgson, K.O., Dey, A. and Szilagyi, R.K., 2005. Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds. Coordination Chemistry Reviews, 249(1–2), pp.97–129. [13] Ma, Q., Prater, J.T., Sudakar, C., Rosenberg, R.A. and Narayan, J., 2012. Defects in room-temperature ferromagnetic Cu-doped ZnO films probed by X-ray absorption spectroscopy. Journal of Physics: Condensed Matter, 24(30), 306002. [14] Zhao, W., Wen, L., Parkin, I.P., Zhao, X. and Liu, B., 2023. Fermi-level shift, electron separation, and plasmon resonance change in Ag nanoparticle-decorated TiO₂ under UV light illumination. Physical Chemistry Chemical Physics, 25(29), pp.20134–20144. [15] Dekker, A.J., 2017. Solid State Physics. Macmillan Indian Ltd. [16] Pines, D., 2018. Elementary Excitations in Solids. CRC Press. [17] Elzinga, E.J. and Reeder, R.J., 2002. X-ray absorption spectroscopy study of Cu²⁺ and Zn²⁺ adsorption complexes at the calcite surface: Implications for site-specific metal incorporation preferences during calcite crystal growth. Geochimica et Cosmochimica Acta, 66(22), pp.3943-3954. [18] Minamimoto, H., Yasuda, K., Zhou, R., Li, X., Yasuda, S. and Murakoshi, K., 2020. Potential energy shift of the Fermi level at plasmonic structures for light-energy conversion determined by graphene-based Raman measurements. The Journal of Chemical Physics, 152(12). [19] Saxena, N.N., Gupta, S.N. and Anihindi, R.G., 1974. Chemical shift of zinc K-absorption edge in some compounds. Journal of Physics and Chemistry of Solids, 35(10), pp.1451–1452. [20] Zhao, X.Z., Jiang, T., Wang, L., Yang, H., Zhang, S. and Zhou, P., 2010. Interaction of curcumin with Zn (II) and Cu (II) ions based on experiment and theoretical calculation. Journal of Molecular Structure, 984(1-3), pp.316-325. [21] Verma, L.P. and Agarwal, B.K., 1968. Shifts in the X-ray K-absorption edge of copper due to chemical effects. Journal of Physics C: Solid State Physics, 1(6), p.1658. [22] Li, Y. and Korzhavyi, P.A., 2017. Physical and chemical properties of Cu (I) compounds with O and/or H. Dalton Transactions, 46(2), pp.529-538. [23] Rößler, N. and Staemmler, V., 2003. Ab initio calculations for the 2s and 2p core level binding energies of atomic Zn, Zn metal, and Zn-containing molecules. Physical Chemistry Chemical Physics, 5(17), pp.3580-3586. [24] Morton, S.M., Silverstein, D.W. and Jensen, L., 2011. Theoretical studies of plasmonics using electronic structure methods. Chemical reviews, 111(6), pp.3962-3994. [25] Halas, N.J., Lal, S., Chang, W.S., Link, S. and Nordlander, P., 2011. Plasmons in strongly coupled metallic nanostructures. Chemical reviews, 111(6), pp.3913-3961. [26] Srivastava, K.S., Singh, S., Gupta, P., Srivastava, A.K., Kumar, V., Husain, M. and Prasad, M.K., 1981. X-ray K-absorption edge shifts due to chemical combination. Pramana, 17(2), pp.187-192. [27] Akbari-Moghanjoughi, M., 2023. Energy Band Structure of Relativistic Quantum Plasmon Excitation. arXiv preprint arXiv:2303.04881. [27] Baker, M.L., Mara, M.W., Yan, J.J., Hodgson, K.O., Hedman, B. and Solomon, E.I., 2017. K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites. Coordination Chemistry Reviews, 345, pp.182–208. [28] Saxena, N.N., Gupta, S.N. and Anihindi, R.G., 1974. Chemical shift of zinc K-absorption edge in some compounds. Journal of Physics and Chemistry of Solids, 35(10), pp.1451–1452. [29] Verma, L.P. and Agarwal, B.K., 1968. Shifts in the X-ray K-absorption edge of copper due to chemical effects. Journal of Physics C: Solid State Physics, 1(6), p.1658. [30] Paterson, P.J.K. and Leckey, R.C.G., 1974. Characteristic energy losses in zinc and cadmium. Journal of Physics F: Metal Physics, 4(6), L156. [31] Velu, S., Suzuki, K., Vijayaraj, M., Barman, S. and Gopinath, C.S., 2005. In situ XPS investigations of Cu₁₋ₓNiₓZnAl mixed metal oxide catalysts used in the oxidative steam reforming of bio-ethanol. Applied Catalysis B: Environmental, 55(4), pp.287–299. [32] Krishchenko, I.M., Manoilov, É.G., Kravchenko, S.A. and Snopok, B.A., 2020. Resonant optical phenomena in heterogeneous plasmon nanostructures of noble metals: a review. Theoretical and Experimental Chemistry, 56(2), pp.67-110. [33] Huang, H.B., Yu, K., Zhang, N., Xu, J.Y., Yu, X.T., Liu, H.X., Cao, H.L., Lü, J. and Cao, R., 2020. Localized surface plasmon resonance enhanced visible-light-driven CO₂ photoreduction in Cu nanoparticle loaded ZnInS solid solutions. Nanoscale, 12(28), pp.15169-15174. [34] Jian, C.C., Zhang, J. and Ma, X., 2020. Cu–Ag alloy for engineering properties and applications based on the LSPR of metal nanoparticles. RSC advances, 10(22), pp.13277-13285. [35] Leon, D.A., Cardoso, C. and Berland, K., 2025. Bulk plasmons in elemental metals. arXiv preprint arXiv:2510.07261. [36] Raether, H. (2006). Excitation of plasmons and interband transitions by electrons. Springer, Berlin, pp. 23–34. [37] Vehse, R.C. and Arakawa, E.T., 1969. Optical and photoemissive properties of nickel in the vacuum-ultraviolet spectral region. Physical Review, 180(3), 695–705. [38] Philipp, H.R. and Ehrenreich, H., 1963. Optical properties of semimetals. Physical Review, 129(4), 1550–1560. [39] Tomaev, V.V., Polishchuk, V.A., Vartanyan, T.A. and Vasil’ev, E.A., 2019. Surface plasmon resonance in zinc nanoparticles. Glass Physics and Chemistry, 45, 238–241. [40] Amekura, H., Shinotsuka, H. and Yoshikawa, H., 2017. Are the triple surface plasmon resonances in Zn nanoparticles true? Nanotechnology, 28(49), 495712. [41] Derkachova, A., Kolwas, K. and Demchenko, I., 2016. Dielectric function for gold in plasmonics applications: size dependence of plasmon resonance frequencies and damping rates for nanospheres. Plasmonics, 11, pp.941–951. [42] Saxena, N.N., Gupta, S.N. and Anihindi, R.G., 1974. Chemical shift of zinc K-absorption edge in some compounds. Journal of Physics and Chemistry of Solids, 35(10), pp.1451–1452. [43] Verma, L.P. and Agarwal, B.K., 1968. Shifts in the X-ray K-absorption edge of copper due to chemical effects. Journal of Physics C: Solid State Physics, 1(6), p.1658. [44] Chaboy, J., Muñoz-Páez, A., Carrera, F., Merkling, P. and Marcos, E.S., 2005. Ab initio X-ray absorption study of copper K-edge XANES spectra in Cu(II) compounds. Physical Review B, 71(13), 134208. [45] Levlev, V.M. and Shvedov, E.V., 2018. Physics of the Solid State, 44(3), 144–149. [46] Matsumoto, Y., Katayama, M., Abe, T., Ohsawa, T., Ohkubo, I., Kumigashira, H. and Koinuma, H., 2010. Chemical trend of Fermi-level shift in transition metal-doped TiO₂ films. Journal of the Ceramic Society of Japan, 118(1383), pp.993–996 [47] Lourenço, M.A., Zeng, J., Jagdale, P., Castellino, M., Sacco, A., Farkhondehfal, M.A. and Pirri, C.F., 2021. Biochar/zinc oxide composites as effective catalysts for electrochemical CO₂ reduction. ACS Sustainable Chemistry & Engineering, 9(15), pp.5445–5453. [48] Gorai, S.K. and Mahto, P., 2013. Correlation between ground state properties and plasmon energy of ternary chalcopyrite semimetals. IOSR Journal of Applied Physics, 3, pp.19–23. [49] Link, S. and El-Sayed, M.A., 1999. Size and temperature dependence of the plasmon absorption of colloidal gold nanoparticles. The Journal of Physical Chemistry B, 103(21), 4212–4217. [50] Brouder, C., Alouani, M. and Arnaud, B., 2004. Electronic structure and X-ray absorption edges of Cu and Zn compounds: Relation to plasmonic and charge-transfer effects. Physical Review B, 70, 045119. [51] Stebunov, Y.V., Yakubovsky, D.I., Fedyanin, D.Y., Arsenin, A.V. and Volkov, V.S., 2018. Superior sensitivity of copper-based plasmonic biosensors. Langmuir, 34(15), pp.4681–4687. [52] Stern, E.A. and Ferrell, R.A., 1960. Surface plasma oscillations of a degenerate electron gas. Physical Review, 120(1), pp.130. [53] Lal, S., Link, S. and Halas, N.J., 2007. Nano-optics from sensing to waveguiding. Nature Photonics, 1(11), pp.641–648. [54] Geetha, P.P., Ramachandran, A. and Nair, S.S., 2020. Tuning of localized surface plasmon resonance in copper–copper oxide core–shell quantum dots for biosensor applications. [55] Cortez-Valadez, M., Bocarando-Chacon, J.G., Hernández-Martínez, A.R., Hurtado, R.B., Alvarez, R.A., Roman-Zamorano, J.F. and Flores-Acosta, M., 2014. Optical properties and radial breathing modes present in Cu amorphous quantum dots obtained by green synthesis. Nanoscience and Nanotechnology Letters, 6(7), pp.580–583. [56] Indhu, A.R., Dharanya, C. and Dharmalingam, G., 2024. Plasmonic copper: ways and means of achieving, directing, and utilizing surface plasmons. Plasmonics, 19(3), pp.1303-1357. [57] Pillai, A.M., Nair, N., Das, M.K. and Ram, S.K., 2025. Strategic approaches to enhance efficiency and commercial feasibility of copper-based surface plasmon resonance sensing. Next Materials, 7, p.100377. [58] Park, B.K., Jeong, S., Kim, D., Moon, J., Lim, S. and Kim, J.S., 2007. Synthesis and size control of monodisperse copper nanoparticles by polyol method. Journal of Colloid and Interface Science, 311(2), pp.417–424. [59] Devasenathipathy, R., Wu, D.Y. and Tian, Z.Q., 2019. Surface plasmon enhanced chemical reactions on metal nanostructures. In: Nanoplasmonics. IntechOpen [60] Martínez-Ruiz, A., Moreno, M.G. and Takeuchi, N., 2003. First-principles calculations of the electronic properties of bulk Cu₂O, clean and doped with Ag, Ni, and Zn. Solid State Sciences, 5(2), pp.291–295. [61] Liu, J., Jalali, M., Mahshid, S. and Wachsmann-Hogiu, S., 2020. Are plasmonic optical biosensors ready for use in point-of-need applications?. Analyst, 145(2), pp.364-384. [62] Reddy, K.R., Hassan, M. and Gomes, V.G., 2015. Hybrid nanostructures based on titanium dioxide for enhanced photocatalysis. Applied Catalysis A: General, 489, 1–16. [63] Hutter, E. and Fendler, J.H., 2004. Exploitation of localized surface plasmon resonance. Advanced Materials, 16(19), 1685–1706. [64] Jiang, Q., Ji, C., Riley, D.J. and Xie, F., 2018. Boosting the efficiency of photoelectrolysis by the addition of non-noble plasmonic metals: Al and Cu. Nanomaterials, 9(1), p.1. [65] Tomaev, V.V., Polishchuk, V.A., Vartanyan, T.A. and Vasil’ev, E.A., 2019. Surface plasmon resonance in zinc nanoparticles. Glass Physics and Chemistry, 45, pp.238–241. [66] Ievlev, V.M. and Shvedov, E.V., 2006. Kinetics of formation of discrete nanostructures during vacuum condensation from a single-component vapor. Physics of the Solid State, 48(1), pp.144-149. [67] Amekura, H., Shinotsuka, H. and Yoshikawa, H., 2017. Are the triple surface plasmon resonances in Zn nanoparticles true? Nanotechnology, 28(49), 495712. [68] Rajamanickam, U., Mylsamy, P., Viswanathan, S. and Muthusamy, P., 2012. Biosynthesis of zinc nanoparticles using actinomycetes for antibacterial food packaging. In: International Conference on Nutrition and Food Sciences IPCBEE, Vol. 39. [69] Singh, S.C. and Gopal, R., 2007. Zinc nanoparticles in solution by laser ablation technique. Bulletin of Materials Science, 30, pp.291–293.
آمار تعداد مشاهده مقاله: 202 تعداد دریافت فایل اصل مقاله: 173

سامانه مدیریت نشریات علمی. قدرت گرفته از سیناوب

پیوندهای مفید

پیوندهای مفید

آمار

Correlation Between Fermi-Energy, Chemical Shifts, and Surface Plasmon Resonance in Cu and Zn Compounds under X-ray Illumination