基于密度泛函理论方法的δ相Pu 5f状态电子结构计算

doi:10.3866/PKU.WHXB2014Ac03

Abstract

Abstract:

First-principle calculations of 5fⁿ (n=0-7) electronic configurations are performed with several density functional theory (DFT) methods to describe the localized/delocalized states and obtain the precise population of the 5f manifold in delta-plutonium (δ-Pu). The results show that spin polarization clearly reduces the cohesive energies of each electronic configuration, and enhances the cohesion properties. For 5f⁰, 5f¹, 5f³, 5f⁴, and 5f⁶ electronic configurations, the cohesive energies obtained by the spin- polarized local density approximation (SP-LDA)+U method are markedly smaller than that by the SP-LDA method when the lattice constant of δ-Pu exceeds 0.475 nm. The cohesive energies calculated with the spin-polarized generalized gradient approximation (SP-GGA)+U method are smaller than that by SP-GGAmethod, except for 5f⁴ and 5f⁶ electronic configurations, and the former trend to coincide with SP-LDA results when the lattice constants are larger than 0.570 nm. For the SP-LDA(GGA)+Umethod, the cohesive energies of 5f0, 5f1, 5f3, 5f4, and 5f6 (5f0, 5f¹, 5f², 5f³, 5f⁵, and 5f⁷) electronic configurations are all equal, while the cohesive energies of 5f², 5f⁵ (5f⁴) electronic configurations are the same as that of the 5f⁷ (5f⁶) electronic configuration. The cohesive energies of 5fn electronic configurations calculated using the other methods are equal. 5f projected densities of states show that spin polarization results in the exchange split behavior of 5f orbitals. Several 5f states are removed from the Fermi level, which lowers the contribution of 5f states to chemical bonding, and enhances the lattice constant, indicating that strong spin polarization induces partial localization of 5f orbitals. The optimized lattice constants obtained by the SP-LDA method are in good agreement with the experimental values, but the SP-GGA+U method sharply overestimates the lattice constant (by up to about 20%).

Key words: 5f state, Electronic structure, Localization, Spin polarization

LI Ru-Song, HE Bin, LI Gang, XU Peng, LU Xin-Cheng, WANG Fei. An Electronic Structure Calculation for 5f States of δ Phase Plutonium Based on the Density Functional Theory Method[J]. Acta Phys. -Chim. Sin. 2015, 31(Suppl), 75-80. doi: 10.3866/PKU.WHXB2014Ac03

References

(1) Söderlind, P.; Landa, A.; Sadigh, B. Phys. Rev. B 2002, 66, 205109. doi: 10.1103/PhysRevB.66.205109
(2) Boettger, J. C. Int. J. Quantum Chem. 2003, 95, 380.
(3) Postnikov, A. V.; Antropov, V. P. Comp. Mat. Sci. 2000, 17, 438. doi: 10.1016/S0927-0256(00)00064-1
(4) Hecker, S. S.; Harbur, D. R.; Zocco, T. G. Prog. Mater. Sci. 2004, 49, 429. doi: 10.1016/S0079-6425(03)00032-X
(5) Wang, Y.; Sun, Y. J. Phys.: Condes. Matter 2000, 12, L311.
(6) Wu, X.; Ray, A. K. Phys. Rev. B 2005, 72, 045115. doi: 10.1103/PhysRevB.72.045115
(7) Gong, H. R.; Ray, A. K. Surf. Sci. 2006, 600, 2231. doi: 10.1016/j.susc.2006.03.021
(8) Kutepov, A. L.; Kutepova, S. G. J. Phys. Condes.: Matt. 2003, 15, 2607. doi: 10.1088/0953-8984/15/17/315
(9) Kollar, J.; Vitos, L.; Skriver, H. L. Phys. Rev. B 1997, 55, 15353. doi: 10.1103/PhysRevB.55.15353
(10) Hay, P. J.; Martin, R. L. J. Chem. Phys.1998, 109, 3875. doi: 10.1063/1.476988
(11) Söderlind, P.; Sadigh, B. Phys. Rev. Lett. 2004, 92, 185702. doi: 10.1103/PhysRevLett.92.185702
(12) Savrasov, S. Y.; Kotliar, G. Phys. Rev. Lett. 2000, 84, 3670. doi: 10.1103/PhysRevLett.84.3670
(13) Sadigh, B.; Wolfer, W. G. Phys. Rev. B 2005, 72, 205122. doi: 10.1103/PhysRevB.72.205122
(14) Shorikov, A. O.; Lukoyanov, A. V.; Korotin, M. A.; Anisimov, V. I. Phys. Rev. B 2005, 72, 024458. doi: 10.1103/PhysRevB.72.024458
(15) Zhu, Z. H.; Meng, D. Q. Acta Phys. Sin. 2011, 60, 040301. [朱正和, 蒙大桥. 物理学报, 2011, 60, 040301]
(16) Shick, A. B.; Drchal, V.; Havela, L. Europhys. Lett. 2005, 69, 588. doi: 10.1209/epl/i2004-10380-5
(17) Johansson, B.; Rosengren, A. Phys. Rev. B 1975, 11, 1367. doi: 10.1103/PhysRevB.11.1367
(18) Savrasov, S. Y.; Kotliar, G.; Abrahams, E. Nature 2001, 410, 793. doi: 10.1038/35071035
(19) Moore, K. T.; Wall, M. A.; Schwartz, A. J.; Chung, B.W.; Shuh, D. K.; Schulze, R. K.; Tobin, J. G. Phys. Rev. Lett. 2003, 90, 196404. doi: 10.1103/PhysRevLett.90.196404
(20) van der Laan, G.; Moore, K. T.; Tobin, J. G.; Chung, B.W.; Wall, M. A.; Schwartz, A. J. Phys. Rev. Lett. 2004, 93, 097401. doi: 10.1103/PhysRevLett.93.097401
(21) Tobin, J. G.; Moore, K. T.; Chung, B.W.; Wall, M. A.; Schwartz, A. J.; van der Laan, G.; Kutepov, A. L. Phys. Rev. B 2005, 72, 085109. doi: 10.1103/PhysRevB.72.085109
(22) Moore, K. T.; van der Laan, G.; Haire, R. G.; Wall, M. A.; Schwartz, A. J. Phys. Rev. B 2006, 73, 033109. doi: 10.1103/PhysRevB.73.033109
(23) Kotliar, G.; Vollhardt, D. Phys. Today 2004, 57, 53.
(24) Dai, X.; Savrasov, S. Y.; Kotliar, G.; Migliori, A.; Ledbetter, H.; Abrahams, E. Science 2003, 300, 953. doi: 10.1126/science.1083428
(25) Wong, J.; Krisch, M.; Farber, D. L.; Occelli, F.; Schwartz, A. J.; Chiang, T. C.; Wall, M.; Boro, C.; Xu, R. Science 2003, 301, 1078. doi: 10.1126/science.1087179
(26) Pourovskii, L. V.; Katsnelson, M. I.; Lichtenstein, A. I.; Havela, L.; Gouder, T.; Wastin, F.; Shick, A. B.; Drchal, V.; Lander, G. H. Europhys. Lett. 2006, 74, 479. doi: 10.1209/epl/i2005-10548-5

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An Electronic Structure Calculation for 5f States of δ Phase Plutonium Based on the Density Functional Theory Method

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