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Cyclic M(SO2) (M=Zn, Cd) and its Anions: Matrix Infrared Spectra and DFT Calculations
Guang-jun Li,Xing Liu,Jie Zhao,Bing Xu,Xue-feng Wang*
Author NameAffiliationE-mail
Guang-jun Li Department of Chemistry, Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University, Shanghai 200092, China  
Xing Liu Department of Chemistry, Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University, Shanghai 200092, China  
Jie Zhao Department of Chemistry, Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University, Shanghai 200092, China  
Bing Xu Department of Chemistry, Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University, Shanghai 200092, China  
Xue-feng Wang* Department of Chemistry, Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University, Shanghai 200092, China xfwang@tongji.edu.cn 
Abstract:
Reaction of laser ablated zinc and cadmium atoms with SO2 molecules was studied by low temperature matrix isolation infrared spectroscopy. Cyclic M(SO2) and anion M(SO2)- (M=Zn, Cd) were produced in excess argon and neon, which were identified by 34SO2 and S18O2 isotopic substitutions. The observed infrared spectra and molecular structures were confirmed by density functional theoretical calculations. Natural charge distributions indicated significant electron transfer from s orbitals of zinc or cadmium metal atom to SO2 ligand and cyclic M(SO2) complexes favored “ion pair” M+(SO2)- formation, which were trapped in low temperature matrices. In addition Zn-O or Cd-O bond in M(SO2) exhibited strong polarized covalent character. Reaction of Hg atom with SO2 was also investigated, but no reaction product was observed, due to the relativistic effect that resulted in the contraction of 6s valence shell and high ionization potential of Hg atom
Key words:  Sulfur dioxide, Matrix isolation, Transition metal, Density functional calcula-tion
FundProject:
环式M(SO2)(M=Zn, Cd)分子及其阴离子的基质隔离红外光谱和密度泛函理论计算
李广君,刘星,赵杰,许兵,王雪峰*
摘要:
激光溅射锌和镉原子与SO2分子反应的低温基质隔离红外光谱实验表明,在氩和氖的惰性基质中,形成了环式M(SO2)分子及其阴离子M(SO2)- (M=Zn, Cd).相关同位素(34SO2和S18O2)替代实验及密度泛函理论计算均证实了这一结果.此外,自然电荷布居分析表明电子从金属锌和镉的s轨道转移到了SO2配体上形成了M+(SO2)-“离子对”复合物,且该分子中的Zn-O键以及Cd-O键均表现出强的极化共价性.而Hg原子在与SO2反应中所表现出来的惰性可由其较强的相对论效应所致的6s价电子层收缩与高电离电位得以解
关键词:  基质隔离,密度泛函理论计算,二氧化硫,过渡金属
DOI:10.1063/1674-0068/26/06/747-754
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