Acta Phys. -Chim. Sin. ›› 2009, Vol. 25 ›› Issue (04): 655-660.doi: 10.3866/PKU.WHXB20090419

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Structures and Vibrational Frequencies of Gas Phase and Solvated Uranyl Complexes UO2L 2-n*an (L=F-, CO2-3, NO-3; n=0-6, a=1, 2)

 GU Jia-Fang, LU Chun-Hai, CHEN Wen-Kai, XU Ying, ZHENG Jin-De   

  1. Department of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China; State Key Laboratory for Surface Physics and Chemistry, Mianyang 621907, Sichuan Province, P. R. China; Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China
  • Received:2008-11-07 Revised:2008-12-19 Published:2009-03-31
  • Contact: CHEN Wen-Kai E-mail:qc2008@fzu.edu.cn

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Abstract:

The geometries and IR frequencies of uranyl complexes were calculated by B3LYP method in density
functional theory (DFT) using the relative effective core potential (RECP) on uraniumand 6-31+G(d) basis set on other elements. Both gaseous and aqueous phases were considered and conductor-like polarized continuum model(CPCM) was used to consider the solvation effect of water. Ligands investigated in the present paper were F-, CO2-3, and NO-3. A linear correlation between the frequency of the O=U=O symmetrical stretching vibration and the number (n) of ligands was established for the above-mentioned ligands according to the following two equations: νs=-Agasn+983 and νs=-Aaqn+821, where Agas and Aaq are characteristic coefficients that represent the shift in vibrational frequency for the addition of each ligand to the uranyl center. Results obtained for F- fit the equations with Agas=53 cm-1 and Aaq=11 cm-1; CO2-3 with Agas=85 cm-1 and Aaq=19 cm-1; NO-3 with Agas=48 cm-1 and Aaq=-10 cm-1. The value of Aaq was found to correspond to the experimental results.

Key words: Uranyl cation, Density functional theory, Relative effective core potential, Solution effect, Vibration frequency