Molecular structure of ErCl3 and YbCl3 according to the data of the simultaneous electron diffraction and mass spectrometric experiment

作者：Giricheva N I^*; Shlykov S A; Girichev G V; Chernova E V; Lapykina E A

来源：Journal of Structural Chemistry, 2009, 50(2): 235-245.

DOI：10.1007/s10947-009-0034-y

• gas-phase electron diffractometry
• mass spectrometry
• erbium trichloride
• ytterbium trichloride
• vapor composition
• molecular structure
• vibration frequencies
• quantum-chemical calculations
• anharmonicity of vibrations

The saturated vapors of ErCl3 and YbCl3 were studied in a simultaneous electron diffraction and mass spectrometric experiment at 1165 K and 1170 K, respectively. In the vapors of these compounds, we found up to 3 mol.% dimers along with the monomers. The parameters of the r (g) effective configuration of the monomer molecules were determined. For ErCl3 and YbCl3, the internuclear distances r (g)(Ln-Cl) were 2.436(5) A... and 2.416(5) A..., and the bond angles a (g)(Cl-Ln-Cl) were 117.0(10)A degrees and 117.2(10)A degrees, respectively. The equilibrium configurations and vibration frequencies of the monomer and dimer molecules were calculated by the HF, B3LYP, and MP2 methods using the combination of the ECPD energy-consistent quasirelativistic core potential, including 4f electrons [Kr4d (10)4f (n) ], and the contracted [5s4p3d] valence basis set for Er and Yb atoms and the MIDIX [4s3p1d] basis set for Cl atoms. The parameters of the effective r (g) configuration of the monomer molecules corresponding to the temperature of the experiment were calculated. The difference between the calculated equilibrium r (e)(Ln-Cl) and temperature-averaged r (g)(Ln-Cl) distances was found to be 0.001-0.002 A... and did not exceed the error of the r (g)(Ln-Cl) parameter determined in the electron diffraction experiment. The experimental parameters of the r (g) structure were shown to be consistent with the idea about the planar equilibrium geometrical configuration of ErCl3 and YbCl3 molecules.

• 出版日期2009-4
• 单位北京化工大学