| [M(Im)2X2]型配合物的Far-IR和Raman光谱的理论研究 |
| Theoretical Study on Far-IR and Raman Spectra of [M(Im)2X2] Type of Metal Complexes |
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| 摘要: 本文用从头计算RHF和密度泛函B3LYP方法以及LanL2DZ，SDD和6-31G(d)基组计算了配合物M(Im)2X2 (Im=imidazole；M=Zn(Ⅱ)，Pd(Ⅱ)，Pt(Ⅱ)；X=F，Cl，Br，I)的几何构型以及Far-IR和Raman振动频率。计算结果表明，对Zn(Ⅱ)配合物而言,B3LYP/6-31G(d)方法得到的几何参数与实验值吻合得最好，B3LYP/SDD次之。在计算Far-IR和Raman振动频率时，发现采用6-31G(d)基组，两种方法计算的结果差别不大。对LanL2DZ和SDD基组而言，对计算结果影响较大的是理论方法，基组影响甚微，个别的振动频率基组影响较大，相比较而言，SDD基组得到的结果更好一些。本文所使用的两种计算方法都能得到与实验值比较吻合的结果，而用从头计算RHF方法计算的结果与实验值更接近一些。在此基础上，预测了Pd(Ⅱ)和Pt(Ⅱ)配合物的Far-IR和Raman振动频率。 |
| 关键词: ab initio RHF B3LYP Far-IR光谱 Raman光谱 二卤素二咪唑金属配合物 |
| 基金项目: |
| Abstract: The geometries and vibrational frequencies of M(Im)2X2 type of complexes (Im=imidazole; M=Zn, Pt, Pd; X=F, Cl, Br, I) have been theoretically calculated using ab initio RHF and density functional B3LYP methods with LanL2DZ, SDD and 6-31G(d) basis sets. The results obtained for Zn(Im)2X2 revealed that the geometries calculated at B3LYP/6-31G(d) level are in the best agreement with the experimental ones, and the values obtained at B3LYP/SDD level are the better. In calculating Far-IR and Raman vibrational frequencies, the results calculated by RHF method and B3LYP method are similar each other with 6-31G(d) basis set. But for LanL2DZ and SDD basis sets, the theoretical methods mainly effect on the vibrational frequencies and the basis sets have neglect effect on these vibrational frequencies except for some exceptions. In comparison of calculated vibrational frequencies with experimental ones, in the far-infrared frequency region, both B3LYP and RHF methods can achieve good results, though the better results are obtained by the RHF method. The Far-IR and Raman vibrational frequencies for the Pd(Ⅱ) and Pt(Ⅱ) complexes are predicted. |
| Keywords: ab initio RHF B3LYP Far-infrared spectra Raman spectra dihalidediimidazole metal complexes |
| 投稿时间：2004-09-01 修订日期：2004-10-21 |
| 摘要点击次数: 1346 |
| 全文下载次数: 1418 |
| 赵春梅,杨高升,缪韧,洪瑾,朱龙根.[M(Im)2X2]型配合物的Far-IR和Raman光谱的理论研究[J].无机化学学报,2005,21(2):151-164. |
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