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Employing hybrid HF/DFT functional in conjunction with the relativistic effective core potential for Pu atoms and all-electron basis set 6-311g（d） for O atoms, the equilibrium geometrical structures of PuO, PuO2 and Pu2O3 molecules are obtained in the geometry optimization. The infrared and Raman spectra are also calculated. The bond lengths and harmonic vibration frequencies of ground states of PuO and PuO2 molecules are all in agreement with available experimental data. In geometry optimization of Pu2O3 molecule, we have tested more than twenty initial structures with different spin multiplicities （1, 3, 5, 7, 9, 11 and 13）. A C2v geometry corresponding to electronic state of 11B2 is considered as the ground state of Pu2O3 molecule. The harmonic frequency, IR intensity, Raman scatting activity and depolarization ratio of Pu2O3 molecule are obtained for the first time in theory. The vibrational modes corresponding to the maximum peaks are assigned for PuO2 and Pu2O3 molecules. In all studied molecules, the charge transfers from Pu to O atoms are found from natural bonding orbital analysis （NBO）. Relative to PuO and PuO2 molecules corresponding to Pu-O single- bond, the interactions between Pu and O in Pu2O3 are much weaker. The spin magnetic moments of studied molecules stem mainly from the 5f atomic orbitals of Pu atoms, but for O atoms the antiparallel spins from 2p atomic orbital are exhibited.
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Keywords:
- plutonium oxides /
- molecular structure and molecular spectra /
- density functional theory /
- relativistic effective core potential（RECP）
[1] ［1］Darleane C H Advance sin. Plutonium Chemistry 1967—2000
[2] ［2］Schreckenbach G,Hay P J, Martin R L 1999 J.Comp.Chem. 20 70
[3] ［3］Hay P J, Martin R L 1998 J.Chem.Phys. 109 3875
[4] ［4］Haschke J M, Allen T H,Morales L A 2000 Los Alamos Science Number 26 252
[5] ［5］Green D W, Reedy G T 1978 J. Chem. Phys. 69 544
[6] ［6］Green D W, Reedy G T 1978 J. Chem. Phys. 69 552
[7] ［7］Person W B, Kim K C, Campbell G M, Dewey H J 1986 J. Chem. Phys. 85 5524
[8] ［8］Haschke J M,Allen T H, 2001 J. Alloys Compd. 320 58
[9] ［9］Gerald Jomard, 2008 Phys. Rev. B 78 075125
[10] ］Sun B, Zhang P 2008 Chin.Phys. B 17 1364
[11] ］Gao T,Zhu Z H,Li G,Sun Y,Wang X L 2004 Chin.J.Chem.Phys.17 554（in chinese）［高涛、朱正和、李赣、孙颖、汪小琳 2004 化学物理学报 17 554］
[12] ］Gao T, Wang H Y,Yi Y G,Tan M L,Zhu Z H,Sun Y,Wang X L,Fu Y B 1999 Acta Phys. Sin.48 2222（in chinese）［高涛、王艳红、易有根、谭明亮、朱正和、孙颖、汪小琳、傅依备 1999 物理学报 48 2222］
[13] ］Gao T,Zhu Z H,Wang X L,Sun Y,Meng D Q 2004 Acta Chim.Sin.62 454（in chinese）［高涛、朱正和、汪小琳、孙颖、蒙大桥 2004 化学学报 62 454］
[14] ］Xiong B T，Meng D Q，Xue W D，Zhu Z H，Jiang G，Wang H Y 2003 Acta Phys. Sin. 52 1617［熊必涛、蒙大桥、薛卫东、朱正和、蒋刚、王红艳 2003 物理学报 52 1617］
[15] ］Meng D Q，Jiang G，Liu X Y，Luo D L，Zhang W X，Zhu Z H 2001 Acta Phys. Sin.50 1268（in chinese）［蒙大桥、蒋刚、刘晓亚、罗德礼、张万箱、朱正和 2001 物理学报 50 1268］
[16] ］Wadt W R 1987 J. Chem. Phys. 86 339
[17] ］Archibong E F,Ray A K 2000 J. Mol. Struct. （Theochem） 530 165
[18] ］Wu X Y, Asok K Ray 2001 Phys. B 301 359
[19] ］Fink J K 1982 Int. J. Thermophys 3 165
[20] ］Gao T, Wang H Y,Huang Z,Zhu Z H,Sun Y,Wang X L,Fu Y B 1999 Acta Phys.-Chim.Sin.15 1082 （in Chinese）［高涛、王艳红、黄整、朱正和、孙颖、汪小琳、傅依备 1999 物理化学学报 15 1082］
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[1] ［1］Darleane C H Advance sin. Plutonium Chemistry 1967—2000
[2] ［2］Schreckenbach G,Hay P J, Martin R L 1999 J.Comp.Chem. 20 70
[3] ［3］Hay P J, Martin R L 1998 J.Chem.Phys. 109 3875
[4] ［4］Haschke J M, Allen T H,Morales L A 2000 Los Alamos Science Number 26 252
[5] ［5］Green D W, Reedy G T 1978 J. Chem. Phys. 69 544
[6] ［6］Green D W, Reedy G T 1978 J. Chem. Phys. 69 552
[7] ［7］Person W B, Kim K C, Campbell G M, Dewey H J 1986 J. Chem. Phys. 85 5524
[8] ［8］Haschke J M,Allen T H, 2001 J. Alloys Compd. 320 58
[9] ［9］Gerald Jomard, 2008 Phys. Rev. B 78 075125
[10] ］Sun B, Zhang P 2008 Chin.Phys. B 17 1364
[11] ］Gao T,Zhu Z H,Li G,Sun Y,Wang X L 2004 Chin.J.Chem.Phys.17 554（in chinese）［高涛、朱正和、李赣、孙颖、汪小琳 2004 化学物理学报 17 554］
[12] ］Gao T, Wang H Y,Yi Y G,Tan M L,Zhu Z H,Sun Y,Wang X L,Fu Y B 1999 Acta Phys. Sin.48 2222（in chinese）［高涛、王艳红、易有根、谭明亮、朱正和、孙颖、汪小琳、傅依备 1999 物理学报 48 2222］
[13] ］Gao T,Zhu Z H,Wang X L,Sun Y,Meng D Q 2004 Acta Chim.Sin.62 454（in chinese）［高涛、朱正和、汪小琳、孙颖、蒙大桥 2004 化学学报 62 454］
[14] ］Xiong B T，Meng D Q，Xue W D，Zhu Z H，Jiang G，Wang H Y 2003 Acta Phys. Sin. 52 1617［熊必涛、蒙大桥、薛卫东、朱正和、蒋刚、王红艳 2003 物理学报 52 1617］
[15] ］Meng D Q，Jiang G，Liu X Y，Luo D L，Zhang W X，Zhu Z H 2001 Acta Phys. Sin.50 1268（in chinese）［蒙大桥、蒋刚、刘晓亚、罗德礼、张万箱、朱正和 2001 物理学报 50 1268］
[16] ］Wadt W R 1987 J. Chem. Phys. 86 339
[17] ］Archibong E F,Ray A K 2000 J. Mol. Struct. （Theochem） 530 165
[18] ］Wu X Y, Asok K Ray 2001 Phys. B 301 359
[19] ］Fink J K 1982 Int. J. Thermophys 3 165
[20] ］Gao T, Wang H Y,Huang Z,Zhu Z H,Sun Y,Wang X L,Fu Y B 1999 Acta Phys.-Chim.Sin.15 1082 （in Chinese）［高涛、王艳红、黄整、朱正和、孙颖、汪小琳、傅依备 1999 物理化学学报 15 1082］
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