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锰氧化物团簇正离子与硫化氢反应的实验与理论研究 (cited: 2)
贾美叶1,2, 何圣贵*1, 葛茂发*1
1.中国科学院化学研究所,北京 100190;2.中国科学院大学,北京100049
摘要:
采用激光溅射法制备了同位素标记的氧化锰团簇正离子Mnm18On+,并研究了其在快速流动反应管中与硫化氢在热碰撞条件下的反应,氧化锰团簇正离子与硫化氢反应前后的质量分布与强度变化由飞行时间质谱仪检测.实验表明,绝大多数氧化锰团簇正离子可与硫化氢发生氧-硫交换反应产生水分子,反应通式为:Mnm18On++H2S→Mnm18On-1S++H218O.通过密度泛函理论计算了氧化锰团簇正离Mn2O2+、Mn2O3+和Mn2O4+与H2S反应的机理,结果显示,在这些反应体系中氧-硫交换反应通道同时具有热力学和动力学优势,印证了实验中观察到的现象.气相团簇研究发现的氧-硫交换反应与相关凝聚相体系反应结果一致
关键词:  团簇,氧-硫交换,反应机理,质谱,密度泛函理论
DOI:10.1063/1674-0068/26/06/679-686
分类号:
基金项目:
Experimental and Theoretical Study of Reactions between Manganese Oxide Cluster Cations and Hydrogen Sulfide (cited: 2)
Mei-ye Jia1,2, Sheng-gui He*1, Mao-fa Ge*1
1.Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;2.University of Chinese Academy of Sciences,
Abstract:
Manganese oxide cluster cations Mnm18On+ were prepared by laser ablation and reacted with hydrogen sulfide (H2S) in a fast flow reactor under thermal collision conditions. A time-of-flight mass spectrometer was used to detect the cluster distributions before and after the interactions with H2S. The experiments suggest that oxygen-for-sulfur (O/S) ex-change reaction to release water took place in the reactor for most of the manganese oxide cluster cations: Mnm18On++H2S→Mnm18On-1S++H218O. Density functional theory cal- culations were performed for reaction mechanisms of Mn2O2+, Mn2O3+, and Mn2O4+. The computational results indicate these O/S exchange reactions are both thermodynamically and kinetically favorable, thus in good agreement with the experimental observations. The O/S exchange reactions identified in this gas-phase cluster study parallel similar behavior of related condensed phase reaction systems.
Key words:  Cluster, Oxygen-for-sulfur exchange, Reaction mechanism, Mass spectrometry, Density functional theory