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The structural and spectroscopic properties for uranium oxides |
| Li Peng(李鹏)a), Jia Ting-Ting(贾婷婷)a), Gao Tao(高涛)a)†, and Li Gan(李赣)b) |
a. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China;
b. National Key Laboratory for Surface Physics and Chemistry, Mianyang 621907, China |
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Abstract The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO$_{2}$, UO$_{3}$, and U$_{2}$O$_{3}$ molecules are systematically investigated using the density functional theory (DFT) with the method of generalized gradient approximation (GGA). The bond lengths and the vibrational frequencies of the ground states of UO, UO$_{2 }$, and UO$_{3 }$ molecules are all in agreement with available experimental data. For U$_{2}$O$_{3 }$ molecules, our calculations indicate that the ground state of the U$_{2}$O$_{3}$ molecule is an $\tilde {\rm X}^{7}$A$_{1}^\prime$ state with $D_{3h }$ (trigonal bipyramid) symmetry ($R_{1}$(U--O)=0.2113 nm, $R_{2}$(U$_{1}$--U$_{2}$)=0.2921 nm, $\angle$U$_{1}$OU$_{2}=87.5$$^\circ$ , dihedral angle $\varTheta $(U,O$_1$,O$_2$,O$_3$)=62.40$^\circ$). The harmonic frequency, the IR intensity and the spin density of the U$_{2}$O$_{3}$ molecule are all obtained for the first time in theory. For the ground state of U$_{2}$O$_{3 }$ molecules, the vibrational frequencies are 178.46 (A$_{1}^\prime$), 276.79 (E$_{1}''$), 310.77 (E$_{1}^\prime$), 396.63 (A$_{2}''$), 579.15 (E$_{1}^\prime$), and 614.98 (A$_{1}^\prime$) cm$^{ - 1}$. The vibrational modes corresponding to the IR maximum peaks are worked out for UO$_{3}$ and U$_{2}$O$_{3 }$ molecules. Besides, the results of Gophinatan--Jug bond order indicate that UO, UO$_{2 }$, and UO$_{3 }$ molecules possess U=O double bonds and that the U$_{2}$O$_{3}$ molecule possesses U--O single bonds and a U--U single bond.
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Received: 10 May 2011
Revised: 01 July 2011
Accepted manuscript online:
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PACS:
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33.20.-t
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(Molecular spectra)
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31.15.ae
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(Electronic structure and bonding characteristics)
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31.15.A-
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(Ab initio calculations)
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Corresponding Authors:
Gao Tao, E-mail:gaotao@scu.edu.cn
E-mail: gaotao@scu.edu.cn
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Cite this article:
Li Peng(李鹏), Jia Ting-Ting(贾婷婷), Gao Tao(高涛), and Li Gan(李赣) The structural and spectroscopic properties for uranium oxides 2012 Chin. Phys. B 21 043301
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