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本文运用密度泛函理论的B3LYP方法, 对钚原子应用LANL2DZ收缩价基函数, 氮、氧原子采用AUG-cc-pVTZ基函数, 分别对PuN, PuO, NO和PuNO体系进行了结构优化, 得到PuNO分子最稳构型为Cv (Pu-N-O), 电子态为6- (基态), 平衡核间距RON=0.12257 nm, RNPu=0.22951 nm, 离解能De=8.10537 eV. 同时优化得到PuNO 分子存在两种亚稳态平衡构型分别为Cv (Pu-O-N), 6- (电子态)和Cs (O-Pu-N), A (电子态), 以及分子体系相应的力学常数等. 拟合出PuN, PuO 和NO 分子的Murrell-Sorbie势能函数, 并使用多体项展式理论得到了PuNO分子的分析势能函数, 其等值势能图准确再现了PuNO分子最稳态构型及两个亚稳态构型的离解能和结构特性, 由此讨论了该分子体系的势能面静态特征.Density functional (B3LPY) method has been utilized to optimize the possible structures of PuN, PuO, NO and PuNO molecules using the contracted valence basis set (LANL2 DZ) for Pu atom, and the AUG-cc-pVTZ basis set for N and O atoms. It is shown that the ground state of the PuNO molecules has Cv (Pu-N-O) symmetry and the ground electronic state is 6-. The equilibrium nuclear distances for Pu-N and N-O bonds in the PuNO molecules are RPuN=0.22951 nm and RNO=0.12257 nm, and the dissociation energy is De=8.10537 eV. Furthermore, the other two metastable states of the PuNO molecules are also obtained, and the electronic states of the two configurations are 6- and A with Cv (Pu-O-N) and Cs (O-Pu-N) symmetry, respectively. Then the Murrell-Sorbie potential energy functions of the PuN, PuO and NO molecules have been simulated and the analytical potential energy function of the PuNO molecules has been derived using the many-body expansion theory. The contours of the potential energy functions reproduce exactly the most stable equilibrium structures, the two metastable state structures as well as the dissociation energy of the PuNO molecules. The molecular static reaction pathway, based on the potential energy function, is also discussed.
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Keywords:
- PuNO /
- molecular structure /
- potential energy function
[1] Lu H, Zhu M, Li Q 2002 Journal of Sichuan Normal University (Nature Science) 3 284 (in Chinese) [卢红, 朱明, 李权 2002 四川师范大学学报(自然科学版) 3 284]
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[7] Xie A D, Zhou L L, Ruan W, Wu D L, Luo W L 2012 Acta Phys. Sin. 61 43302 (in Chinese) [谢安东, 周玲玲, 阮文, 伍东兰, 罗文浪 2012 61 43302]
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[11] Yuan L, Fan Q C, Sun W G, Fan Z X, Feng H 2014 Acta Phys. Sin. 63 043102 (in Chinese) [袁丽, 樊群超, 孙卫国, 范志祥, 冯灏 2014 63 043102]
[12] Clavaguérasarrio C, Vallent V, Maynau D, Marsden C J 2004 J. Chem. Phys. 121 5312
[13] Li Q, Wang H Y, Zhu Z H 2003 Acta Chim. Sin. 12 1930 (in Chinese) [李权, 王红艳, 朱正和 2003 化学学报 12 1930]
[14] Xiong X L, Wei H Y, Chen W 2012 Acta Phys. Sin. 61 13401 (in Chinese) [熊晓玲, 魏洪源, 陈文 2012 61 13401]
[15] Gao T, Zhu Z H, Li G, Sun Y, Wang X L 2004 Chinese J. Chem. Phys. 17 554 (in Chinese) [高涛, 朱正和, 李赣, 孙颖, 汪小琳 2004 化学 17 554]
[16] Zeng H, Zhao J 2012 Chin. Phys. B 21 78202
[17] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R 2003 Gaussian 03 (Revision B.02) Gaussian Inc. Pittsburgh PA
[18] Hay P J, Wadt W R 1985 J. Chem. Phys. 82 299
[19] Masataka M, Keizo I 1989 Jpn. J. Appl. Phys. 28 317
[20] Herzberg G 1950 Molecular Spectra and Molecular structure (Vol.1) (New York: Van Nostrand Reinhold) p558
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[1] Lu H, Zhu M, Li Q 2002 Journal of Sichuan Normal University (Nature Science) 3 284 (in Chinese) [卢红, 朱明, 李权 2002 四川师范大学学报(自然科学版) 3 284]
[2] Li Q, Wang H Y, Zhu Z H 2001 Journal of Atomic and Molecular Physics 4 396 (in Chinese) [李权, 王红艳, 朱正和 2001 原子分子 4 396]
[3] Pepper M, Bursten B E 1991 Chem. Rev. 91 719
[4] Gagliardi L, Roos B O 2007 Chem. Soc. Rev. 36 893
[5] Valerie V, Peter M, Ulf W, Ingmar G 2006 Them. Chem. Acc. 115 145
[6] Heaven M C 2006 Phys. Chem. Chem. Phys. 8 4497
[7] Xie A D, Zhou L L, Ruan W, Wu D L, Luo W L 2012 Acta Phys. Sin. 61 43302 (in Chinese) [谢安东, 周玲玲, 阮文, 伍东兰, 罗文浪 2012 61 43302]
[8] Yang Z J, Gao Q H, Li J, Linghu R F, Guo Y D, Cheng X L, Zhu Z H, Yang X D 2011 Chin. Phys. B 20 53102
[9] Zhang H, Tian D L, Yan S Y 2014 Chin. Phys. B 23 93101
[10] Zhu Z H, Yu H G 1997 Molecular Structure and Potential Energy Function (Beijing: Science Press) (in Chinese) pp130-132 [朱正和, 俞华根 1997 分子结构与分子势能函数(北京: 科学出版社)] 第130-132页
[11] Yuan L, Fan Q C, Sun W G, Fan Z X, Feng H 2014 Acta Phys. Sin. 63 043102 (in Chinese) [袁丽, 樊群超, 孙卫国, 范志祥, 冯灏 2014 63 043102]
[12] Clavaguérasarrio C, Vallent V, Maynau D, Marsden C J 2004 J. Chem. Phys. 121 5312
[13] Li Q, Wang H Y, Zhu Z H 2003 Acta Chim. Sin. 12 1930 (in Chinese) [李权, 王红艳, 朱正和 2003 化学学报 12 1930]
[14] Xiong X L, Wei H Y, Chen W 2012 Acta Phys. Sin. 61 13401 (in Chinese) [熊晓玲, 魏洪源, 陈文 2012 61 13401]
[15] Gao T, Zhu Z H, Li G, Sun Y, Wang X L 2004 Chinese J. Chem. Phys. 17 554 (in Chinese) [高涛, 朱正和, 李赣, 孙颖, 汪小琳 2004 化学 17 554]
[16] Zeng H, Zhao J 2012 Chin. Phys. B 21 78202
[17] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R 2003 Gaussian 03 (Revision B.02) Gaussian Inc. Pittsburgh PA
[18] Hay P J, Wadt W R 1985 J. Chem. Phys. 82 299
[19] Masataka M, Keizo I 1989 Jpn. J. Appl. Phys. 28 317
[20] Herzberg G 1950 Molecular Spectra and Molecular structure (Vol.1) (New York: Van Nostrand Reinhold) p558
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