| 锌族和钛族卤化物振动光谱的理论计算 |
| Theoretical Calculation of Vibrational Frequencies for Halides of Zinc and Titanium Groups |
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| 摘要: 采用ab initio RHF,MP2和B3LYP方法以及LanL2DZ和SDD基组计算了四面体锌族卤素阴离子化合物(MX42-,M=Zn(Ⅱ),Cd(Ⅱ),Hg(Ⅱ);X=F-,Cl-,Br-,I-)和钛族卤化物(MX4,M=Ti(Ⅳ),Zr(Ⅳ),Hf(Ⅳ);X=F-,Cl-,Br-,I-)的几何构型和振动频率。计算结果表明,LanL2DZ基组是合适的基组,能得到合理的电荷分布,几何参数以及振动频率。在锌族卤化物的计算中发现,角弯曲振动频率与实测值相当一致,键伸缩振动频率略为偏低,这主要是由于计算的键长略为偏长所致。MP2方法计算的振动频率更接近于实测值。在钛族卤化物的计算中,三种计算方法都相当地再现了实测值,而以B3LYP方法更为满意。 |
| 关键词: 锌族卤化物 钛族卤化物 振动光谱 理论计算 |
| 基金项目: |
| Abstract: The geometries and vibrational frequencies of halide anions of zinc group (MX42-, M=Zn(Ⅱ), Cd(Ⅱ), Hg(Ⅱ); X=F-, Cl-, Br-, I-) and halides of titanium group (MX4, M=Ti(Ⅳ), Zr(Ⅳ), Hf(Ⅳ); X=F-, Cl-, Br-, I-) have been theoretically calculated using ab initio RHF, MP2 and B3LYP methods with LanL2DZ and SDD basis sets. The results calculated revealed that LanL2DZ basis set is a satisfied one for obtaining reasonable population of charge on the metals, geometry parameters and vibrational frequencies. In MX42- compounds, it was found that the calculated frequencies of the bent vibrations associated with angles are in good agreement with the experimental values, and the frequencies of bond stretching are lower than that of observation, due to the overestimation of bond lengths. The vibrational frequencies calculated at MP2/LanL2DZ level are more reached to the experimental values. In MX4 compounds, three methods with same LanL2DZ basis set reappeared the measured values with a sufficient accuracy, and more satisfied results are obtained with B3LYP method. |
| Keywords: zinc group halides titanium group halides vibrational spectra theoretical calculation |
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| 陶寒冰,张宇,张琳,孙晓娟,朱龙根.锌族和钛族卤化物振动光谱的理论计算[J].无机化学学报,2002,18(7):671-678. |
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