[M(Im)_2X_2]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)_2X_2] Type of Metal Complexes

作　　者：赵春梅[1] 杨高升[1] 缪韧[1] 洪瑾[1] 朱龙根[1] 

机构地区：[1]南京大学配位化学国家重点实验室,南京210093

出　　处：《无机化学学报》2005年第2期151-164,共14页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20271027;20231010)

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=imida-zole;M=Zn(II),Pd9(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髤配合物而言,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Ra-man振动频率。The geometries and vibrational frequencies of M(Im)(2)X-2 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)(2)X-2 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.

关 键 词：基组 B3LYP Zn(Ⅱ)配合物 振动频率 RAMAN光谱 密度泛函 几何构型 IR 吻合 RHF 

分 类 号：O641.121[理学—物理化学] O643.38[理学—化学]