Article, Comparative assessment of exchange-correlation functionals for structural, electronic, and optical properties of rhombohedral Bi0.5Na0.5TiO3
Comparative assessment of exchange-correlation functionals for structural, electronic, and optical properties of rhombohedral Bi0.5Na0.5TiO3
DOI:
https://doi.org/10.65273/hhit.jna.2026.2.3.047Keywords:
BNT, DFT, ab-initio, calculation, exchange-correlation functionals, comparisonAbstract
A systematic first-principles investigation was performed to evaluate the performance of LDA and various GGA functionals (PBE, RPBE, PBESol, PW91, WC) on the structural, electronic, and optical properties of rhombohedral Bi0.5Na0.5TiO3(BNT). The results reveal that while PBESol and WC yield superior lattice parameters, GGA-PBE and GGA-PW91 provide the most consistent overall description of structural properties, direct bandgap energies, and optical absorption spectra. LDA severely underestimates lattice constants and bandgaps, whereas RPBE overestimates lattice parameters. Analysis of partial density of states indicates that the valence band is dominated by O-2p and Ti-3d hybridization, while the conduction band mainly consists of Ti-3d and Bi-6p states. Overall, GGA-PBE emerges as the most reliable functional for studying pristine and modified BNT-based materials.
Downloads
References
[1] G. A. Smolenskii, A. I. Agranovskaya, (1961). New ferroelectrics of complex composition. IV. Soviet Physics-Solid State, 2, 2651-2654.
[2] W. Zhu, Z.Y. Shen, W. Deng, K. Li, W. Luo, F. Song, X. Zeng, Z. Wang, Y. Li, (2024). A review: (Bi,Na)TiO3 (BNT)-based energy storage ceramics. Journal of Materiomics, 10(1), 86-123. https://doi.org/10.1016/j.jmat.2023.05.002
[3] S. B. Vakhrushev, V.A. Isupov, B.E. Kvyatkovsky, N.M. Okuneva, I.P. Pronin, G.A. Smolensky, P.P. Syrnikov, (1985). Phase transitions and soft modes in sodium bismuth titanate. Ferroelectrics, 63(1), 153-160. https://doi.org/10.1080/00150198508221396
[4] G. O. Jones, P. A. Thomas, (2002). Investigation of the structure and phase transitions in the novel A-site substituted distorted perovskite compound Na(0.5)Bi(0.5)TiO(3). Acta Crystallogr B, 58(Pt2), 168-178. https://doi.org/10.1107/s0108768101020845
[5] M. Christensen, M. A. Einarsrud, T. Grande, (2017). Fabrication of Lead-Free Bi0.5Na0.5TiO₃ Thin Films by Aqueous Chemical Solution Deposition. Materials, 10(2), 213.
https://doi.org/10.3390/ma10020213
[6] S.-E. Park, S.-J. Chung, I.-T. Kim, (1996). Ferroic Phase Transitions in (Na1/2Bi1/2)TiO3 Crystals. Journal of the American Ceramic Society, 79(5), 1290-1296.
https://doi.org/10.1111/j.1151-2916.1996.tb08586.x
[7] D. D. Dung, N.H. Lam, L.T.K. Phuong, N.H. Thoan, L.H. Bac, D.T. Trang, P.V. Vinh, N.D. Quan, D.Q. Van, (2021). Optical properties of a new (1−x)Bi1/2Na1/2TiO3 + xPr1/2Na1/2TiO3 solid solution system. Materials Letters, 302, 130381. https://doi.org/10.1016/j.matlet.2021.130381
[8] Dang Duc Dung, Nguyen Hoang Thoan, Nguyen Quoc Dung, Nguyen Huu Lam, Vu Tien Lam, Pham Van Vinh, Pham Dinh Luong, Duong Quoc Van, (2022). Synthesis and Characterization of (1−x)Bi1/2Na1/2TiO3+xSrNiO3-δ Solid Solution System. Journal of Electronic Materials, 51(6), 2716-2731. https://doi.org/10.1007/s11664-022-09534-6
[9] Dang Duc Dung, Nguyen Hoang Thoan, Nguyen Huu Lam, Do Duc Tho, Vu Tien Lam, Nguyen Thi Trang, Duong Quoc Van, (2022). Optical properties of a new binary lead-free ferroelectric semiconductor Bi1/2Na1/2 TiO3–Nd1/2Na1/2TiO3 solid solution system. Applied Physics A, 128(9), 798.
https://doi.org/10.1007/s00339-022-05910-5
[10] J. A. Dawson, H. Chen, I. Tanaka, (2015). Crystal structure, defect chemistry and oxygen ion transport of the ferroelectric perovskite, Na0.5Bi0.5TiO3: insights from first-principles calculations. Journal of Materials Chemistry A, 3(32), 16574-16582. https://doi.org/10.1039/c5ta03705k
[11] F. Yang, M. Li, L. Li, P. Wu, E. Pradal-Velázquez, D. C. Sinclair, (2018). Defect chemistry and electrical properties of sodium bismuth titanate perovskite. Journal of Materials Chemistry A, 6(13), 5243-5254. https://doi.org/10.1039/c7ta09245h
[12] M. H. Ridzwan, M.K. Yaakob, M.F.M. Taib, A.M.M. Ali, O.H. Hassan, M.Z.A. Yahya, (2018). Structural, Electronic and Elastic Properties of rhombohedral phase Bi0.5Na0.5TiO3 Using Density Functional Theory. International Journal of Electroactive Materials, 6, 36-41.
https://www.electroactmater.com/index.php/volume-6-2018?id=60&subid=311
[13] Nguyen Hoang Linh, Nguyen Hoang Tuan, Dang Duc Dung, Phung Quoc Bao, Bach Thanh Cong, Le Thi Hai Thanh, (2019). Alkali metal-substituted bismuth-based perovskite compounds: A DFT study. Journal of Science: Advanced Materials and Devices, 4(3), 492-498.
https://doi.org/10.1016/j.jsamd.2019.06.005
[14] H. Lü, S. Wang, X.S. Wang, (2014). The electronic properties and lattice dynamics of (Na0.5Bi0.5)TiO3: From cubic to tetragonal and rhombohedral phases. Journal of Applied Physics, 115(12), 124107. https://doi.org/10.1063/1.4869733
[15] L. Ju, et al., (2016). First-Principles Study of Magnetism in Transition Metal Doped Na0.5Bi0.5TiO3 System. Chinese Journal of Chemical Physics, 29(4), 462-466. https://doi.org/10.1063/1674-0068/29/cjcp1602023
[16] M. Zeng, S. W. Or, H. L. W. Chan, (2010). First-principles study on the electronic and optical properties of Na0.5Bi0.5TiO3 lead-free piezoelectric crystal. Journal of Applied Physics, 107(4), 043513.
https://doi.org/10.1063/1.3309407
[17] Chatta Wahiba, Brahim Lagoun, Lidjici Hamza, Abdelhakim Chadli, Abderahmane Cheriet, Hichem Farh, Hamadi Khemakhem, Khenchoul Salah, (2019). TB-mBJ Calculations of Structural and Optoelectronic Properties of the Rhombohedral Phase of Bismuth Sodium Titanate (Bi0.5Na0.5)TiO3. Solid State Phenomena, 297, 165-172. https://doi.org/10.4028/www.scientific.net/SSP.297.165
[18] D. Q. Van, L. M. Thu, Ş. Ţălu, (2026). First-principles investigation of structural, electronic and optical properties of rhombohedral Na0.5Bi0.5TiO3. Journal of Nanomaterials and Applications, 2(1), 50-64. https://doi.org/10.65273/hhit.jna.2026.2.1.029
[19] Dang Duc Dung, Vu Tien Lam, Nguyen Huu Lam, Duong Quoc Van, Hoang Thoan Nguyen, Nguyen Hoang Linh, Nguyen Ngoc Trung, (2024). Surface ferromagnetism of lead-free ferroelectric bismuth sodium titanate materials. Communications in Physics, 34(1), 83-97. https://doi.org/10.15625/0868-3166/19184
[20] Quoc-Van Duong, Anh-Duong Nguyen, Cao-Khang Nguyen, Ngoc-Anh Nguyen Thi, Chinh-Cuong Nguyen, Duc-Dung Dang, Tien-Lam Vu, Minh-Thu Le, (2024). An ab initio calculation on the structural, electronic and magnetic properties of Ni-doped Bi0.5Na0.5TiO3. HPU2 Journal of Science: Natural Sciences and Technology, 3(3), 10-19. https://doi.org/10.56764/hpu2.jos.2024.3.3.10-19
[21] Vu Tien Lam, Nguyen Huu Lam, Nguyen Hoang Linh, Duong Quoc Van, Dang Duc Dung, (2026). Influence of complex antisite defects in structural distortion, electrical and optical properties of Bi0.5Na0.5TiO3(110) surface: A DFT investigation. Communications in Physics. 36 (3), 157-172 https://doi.org/10.15625/0868-3166/23659
[22] S. F. Yuk, et al., (2017). Towards an accurate description of perovskite ferroelectrics: exchange and correlation effects. Sci Rep, 7, 43482. https://doi.org/10.1038/srep43482
[23] P. Borlido, et al., (2019). Large-Scale Benchmark of Exchange-Correlation Functionals for the Determination of Electronic Band Gaps of Solids. J Chem Theory Comput, 15(9), 5069-5079. https://doi.org/10.1021/acs.jctc.9b00322
[24] Duong Quoc Van, Thoan Hoang Nguyen, Nguyen Huu Lam, Vu Tien Lam, Nguyen Ngoc Trung, Ngo Duc Quan, Dang Duc Dung, (2022). Fabrication and Optical Properties of Rare-Earth-Sm-Doped Lead-Free Ferroelectric Bi0.5Na0.5TiO3 Materials. Proceedings of the International Conference on Advanced Mechanical Engineering, Automation, and Sustainable Development 2021 (AMAS2021), Springer International Publishing: Cham.
[25] P. Borlido, P. Borlido, J. Doumont, F. Tran, M. A. L. Marques, S. Botti, (2020). Validation of Pseudopotential Calculations for the Electronic Band Gap of Solids. J Chem Theory Comput, 16(6), 3620-3627. https://doi.org/10.1021/acs.jctc.0c00214
[26] Y. Shen, J. Cai, H.-C. Ding, X.-W. Shen, Y.-W. Fang, W.-Y. Tong, X.-G. Wan, Q. Zhao, C.-G. Duan, (2019). Role of Lone-Pairs in Driving Ferroelectricity of Perovskite Oxides: An Orbital Selective External Potential Study. Advanced Theory and Simulations, 2(6), 1900029.
https://doi.org/10.1002/adts.201900029
[27] C. Linderälv, A. Lindman, P. Erhart, (2017). A Unifying Perspective on Oxygen Vacancies in Wide Band Gap Oxides. The Journal of Physical Chemistry Letters, 9(1), 222-228.
https://doi.org/10.1021/acs.jpclett.7b03028
[28] M. D. Segall, Philip J. D. Lindan, M. J. Probert, C. J. Pickard, P. J. Hasnip, S. J. Clark, M. C. Payne, (2002). First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys. Condens. Matter, 14, 2717-2744. https://doi.org/10.1088/0953-8984/14/11/301
[29] J. P. Perdew, A. Zunger, (1981). Self-interaction correction to density-functional approximations for many-electron systems. Phys. Rev. B, 23(10), 5048. https://doi.org/10.1103/PhysRevB.23.5048
[30] D. M. Ceperley, B. J. Alder, (1980). Ground State of the Electron Gas by a Stochastic Method. Physical Review Letters, 45(7), 566-569. https://doi.org/10.1103/PhysRevLett.45.566
[31] J. P. Perdew, K. Burke, M. Ernzerhof, (1996). Generalized Gradient Approximation Made Simple. Phys. Rev. Lett., 77(18), 3865. https://doi.org/10.1103/PhysRevLett.77.3865
[32] B. Hammer, L. B. Hansen, J. K. Nørskov, (1999). Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Physical Review B, 59(11), 7413-7421. https://doi.org/10.1103/PhysRevB.59.7413
[33] John P. Perdew, Adrienn Ruzsinszky, Gábor I. Csonka, Oleg A. Vydrov, Gustavo E. Scuseria, Lucian A. Constantin, Xiaolan Zhou, Kieron Burke, (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Physical Review Letters, 100(13), 136406. https://doi.org/10.1103/PhysRevLett.100.136406
[34] Y. Wang, J. P. Perdew, (1991). Correlation hole of the spin-polarized electron gas, with exact small-wave-vector and high-density scaling. Physical Review B, 44(24), 13298-13307.
https://doi.org/10.1103/PhysRevB.44.13298
[35] Z. Wu, R. E. Cohen, (2006). More accurate generalized gradient approximation for solids. Phys. Rev. B, 73, 235116. https://doi.org/10.1103/PhysRevB.73.235116
[36] D. Vanderbilt, (1990). Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Physical Review B, 41(11), 7892-7895. https://doi.org/10.1103/PhysRevB.41.7892
[37] C. G. Broyden, (1970). The Convergence of a Class of Double-rank Minimization Algorithms 1. General Considerations. IMA Journal of Applied Mathematics, 6(1), 76-90.
https://doi.org/10.1093/imamat/6.1.76
[38] R. Fletcher, (1970). A new approach to variable metric algorithms. The Computer Journal, 13(3), 317-322. https://doi.org/10.1093/comjnl/13.3.317
[39] D. Goldfarb, (1970). A Family of Variable-Metric Methods Derived by Variational Means. Mathematics of Computation, 24(109), 23-26. https://doi.org/10.1090/S0025-5718-1970-0258249-6
[40] D. F. Shanno, (1970). Conditioning of Quasi-Newton Methods for Function Minimization. Mathematics of Computation, 24(111), 647-656. https://doi.org/10.2307/2004840
[41] H. J. Monkhorst, J. D. Pack, (1976). Special points for Brillouin-zone integrations. Phys. Rev. B, 13(12), 5188. https://doi.org/10.1103/PhysRevB.13.5188
[42] D. D. Dung, N. H. Thoan, N. Q. Dung, P. V. Vinh, N. H. Lam, V. T. Lam, P. D. Luong, D. Q. Van, (2022). Magnetic Properties of a (1−x)Bi0.5Na0.5TiO3+xCaNiO3-δ Solid Solution System Prepared by Sol–Gel Technique. Journal of Electronic Materials, 51(5), 1905-1921.
https://doi.org/10.1007/s11664-022-09457-2
[43] Dang Duc Dung, Nguyen Hoang Thoan, Nguyen Quoc Dung, Nguyen Huu Lam, Pham Van Vinh, Vu Tien Lam, Pham Dinh Luong, Duong Quoc Van, (2022). Structural, optical, and magnetic properties of a new complex (1−x)Bi1/2Na1/2TiO3 + xMgNiO3−δ solid solution system. Applied Physics A, 128(2), 129.
https://doi.org/10.1007/s00339-021-05255-5
[44] D. L. Wood, J. Tauc, (1972). Weak Absorption Tails in Amorphous Semiconductors. Physical Review B, 5(8), 3144-3151. https://doi.org/10.1103/PhysRevB.5.3144
[45] B. Kharroubi, M. Bousmaha, R. Naceur, (2022). Combination of optical properties acquired by first principles calculations with the empirical Tauc method for determining the band gap energy of alkaline-earth metal oxides: MO (M = Be, Mg, Ca, Sr, Ba). Journal of Computational Methods in Sciences and Engineering, 22(3), 1013-1022. https://doi.org/10.3233/JCM-220001
[46] A. Diebold, T. Hofmann, (2021). Excitons and Excitonic Effects During Optical Transitions. Optical and Electrical Properties of Nanoscale Materials, Springer International Publishing: Cham, 149-177. https://doi.org/10.1007/978-3-030-80323-0_5
[47] H.-X. Zhong, S. Gao, J.-J. Shi, L. Yang, (2015). Quasiparticle band gaps, excitonic effects, and anisotropic optical properties of the monolayer distorted 1T diamond-chain structures ReS2 and ReSe2. Physical Review B, 92(11), 115438. https://doi.org/10.1103/PhysRevB.92.115438
[48] D. D. Dung, N. T. Hung, D. Odkhuu, (2019). Magnetic and optical properties of MgMnO3--modified Bi0.5Na0.5TiO3 materials. Journal of Magnetism and Magnetic Materials, 482, 31-37.
https://doi.org/10.1016/j.jmmm.2019.03.029
[49] M. Zeng, S. W. Or, H. L. W. Chan, (2010). First-principles study on the electronic and optical properties of Na0.5Bi0.5TiO3 lead-free piezoelectric crystal. Journal of Applied Physics, 107(4), 043513. https://doi.org/10.1063/1.3309407
[50] M. Sharma, M. Sierka, (2024). Optical Gaps of Ionic Materials from GW/BSE-in-DFT and CC2-in-DFT. Journal of Chemical Theory and Computation, 20(21), 9592-9605.
Downloads
Published
Data Availability Statement
The data that support the findings of this study are available from the corresponding authors upon reasonable request.
Issue
Section
License
Copyright (c) 2026 Le Minh Thu, Nguyen Phuong Thao, Duong Quoc Van (Author)
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
1. Grant of License
The Author(s) hereby grant to the Publisher a non-exclusive, perpetual, worldwide, royalty-free, and irrevocable license to publish, reproduce, distribute, and display the Work in all forms and media, whether now known or hereafter developed. This includes but is not limited to print, online, and digital formats. The Publisher may also license the Work to third parties for inclusion in databases, repositories, and other platforms.
2. Author's Warranties
-The Author(s) warrant and represent that:
-The Work is an original creation of the Author(s).
-The Author(s) have the full power and authority to enter into this Agreement and to grant the rights granted herein.
-The Work has not been previously published or licensed for publication in any other journal or book.
-The Work does not infringe upon any copyright, trademark, privacy right, or other proprietary right of any third party.
-All necessary permissions for the use of third-party materials (e.g., figures, tables) have been obtained by the Author(s) and are properly credited in the Work
3. Author's Rights
-The Author(s) retain the following rights:
-The right to use the Work for their own personal, academic, and research purposes, including posting it on their personal website or institutional repository, provided that the published version is not used and the original publication is acknowledged.
-The right to include the Work, in part or in full, in future works of their own (e.g., books, dissertations), provided that proper credit is given to the original publication in this journal.
Journal of Nanomaterials and Applications (JNA)
Add: 14-15A, 7th floor, Charmvit Tower building, 117 Tran Duy Hung, Trung Hoa, Hanoi, 100000, Vietnam
Phone: 084+0904526939 Email: jna.com.vn@gmail.com / jna@jna.com.vn Website: jna.com.vn
