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Reactions of Group V Metal Atoms with Hydrogen Sulfide:Argon Matrix Infrared Spectra and Theoretical Calculations
Jie Zhao,Bing Xu,Wen-jie Yu,Xue-feng Wang
Author NameAffiliationE-mail
Jie Zhao Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, Shanghai 200092, China  
Bing Xu Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, Shanghai 200092, China  
Wen-jie Yu Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, Shanghai 200092, China  
Xue-feng Wang Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, Shanghai 200092, China xfwang@tongji.edu.cn 
Abstract:
The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H-S bond of H2S to form the HMSH molecules (M=V, Nb, Ta), which rearranged to H2MS molecules on annealing for Nb and Ta. The HMSH molecule can also further react with another H2S to form the H2M(SH)2 molecules. These new molecules were identified on the basis of the D2S and H234S isotopic substitutions. DFT (B3LYP and BPW91) theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal dihydrido complexes and molecules. Reaction mechanism for formation of group V dihydrido complex was investigated by DFT internal reaction coordinate calculations. The dissociation of HVSH gave VS+H2 on broad band irradiation and reverse reaction happened on annealing. Based on B3LYP calculation releasing hydrogen from HVSH is endothermic only by 13.5 kcal/mol with lower energy barrier of 16.9 kcal/mol.
Key words:  Hydrogen sulfide  Matrix isolation  Transition metal  Density functional
FundProject:
基质隔离红外光谱结合理论计算研究第五族金属原子和硫化氢反应
赵杰,许兵,俞文杰,王雪峰
摘要:
利用基质隔离红外光谱结合理论计算,研究了激光溅射获得的第五族金属原子和硫化氢分子的反应. 结果表明金属原子插入H2S的H-S化学键形成HMSH分子(M=V,Nb,Ta). 对Nb和Ta该HMSH分子重排为H2MS分子. HMSH分子和H2S进一步反应生成H2M(SH)2分子. 通过D2S和H234S同位素标定确定了产物的分子结构,同时我们用DFT(B3LYP和BPW91)理论计算预测了产物分子的能量、结构和振动频率. 通过DFT IRC计算研究了第五族金属原子和2S分子的反应机理. HVSH分子通过光照解离为VS和H2,然后通过退火可以发生VS和H2复合反应. 计算表明HVSH释放H2需要16.9 kcal/mol的活化能及吸热13.5 kcal/mol.
关键词:  硫化氢  基质隔离  过渡金属  DFT理论计算
DOI:10.1063/1674-0068/29/cjcp1511233
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