(μ-L1)(μ-L2)十羰基合三锇电子光谱的含时从头计算

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Abstract Ab initio method was used to optimize the molecular geometry for a series of clusters (μ-L1)(μ-L2)- decacarbonyltriosmium[L1,L2=H,Cl,Br,I] at HF/CEP-4G level. The related chemical properties of clusters,in particular,the regularities of the bridge halogen effects on spectroscopic properties and bonding properties were discussed. The calculation results of the frontier molecular orbital showed that M—M bonds were mainly composed of s and d atomic orbitals. From Cl to I,with the atom number of bridge ligand increasing,HOMO and NHOMO orbitals on the O_s3(CO)₁₀(μ-L)₂ clusters and HOMO on the O_s3(CO)₁₀(μ-H)(μ-L) clusters become higher,while Δε_L-H and Δε_L-NH energies become lower,so the authors predicted that the electronic absorption bands of clusters are shifted to infrared region. Excited states of clusters calculated with TDHF show that the transition of cluster O_s3(CO)₁₀(μ-H)₂(I) is mainly π→σ^* and σ→σ^*,while the electronic absorption of other clusters O_s3(CO)₁₀(μ-H)(μ-L) [L=Cl,Br,I] and O_s3(CO)₁₀(μ-L)₂[L=Cl,Br] is mainly from σ→σ^* transition. From Cl to I,with the atom number of bridge ligand increasing,the electronic absorption band of cluster is shifted to infrared region,and also the absorption becomes weaker.

Key words：(μ-L1)(μ-L2)-decacarbonyltriosmium;TDHF;Frontier molecular orbital;Electronic absorption spectra

Received: 2006-03-06 Accepted: 2006-05-18

ZTFLH:

O641.4

Corresponding Authors: ZENG Rong-ying E-mail: zengrongying2003@yahoo.com.cn

Cite this article:

ZENG Rong-ying,TANG Wen-qing,KUANG Dai-zhi, et al. TDHF Study of Electronic Absorption Spectrum of (μ-L1)(μ-L2)-Decacarbonyl Triosmium[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(07): 1271-1275.

URL:

https://www.gpxygpfx.com/EN/Y2007/V27/I07/1271

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