Experimental and Theoretical Study of Reactions between Manganese Oxide Cluster Cations and Hydrogen Sulfide

锰氧化物簇阳离子 Mn m 18O n + 被激光脱离准备并且在热碰撞条件下面在一个快流动反应堆与氢硫化物(H2S ) 反应了。一个 timeofflight 团分光计被用来在和 H2S 的相互作用前后检测簇分布。实验建议释放水的 oxygenforsulfur (O/S ) 交换反应为大多数锰氧化物簇阳离子发生在反应堆：Mn m 18O n ++H2SMn m 18O n1S++H2 18O。密度功能的理论计算为 Mn2O2 ++H2S， Mn2O3 ++H2S，和 Mn2O4 ++H2S 的反应机制被执行。计算结果显示这些 O/S 交换反应热力学地并且运动地是有利的，这样在对试验性的观察的好同意。在这 gasphase 簇识别的 O/S 交换反应学习相关压缩阶段反应系统的平行类似的行为。

Manganese oxide cluster cations Mnm180n＋ 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： MnmlSOn＋＋H2S→Mnm18On-1S＋＋H218O. Density functional theory cal- culations were performed for reaction mechanisms of Mn202＋＋H2S, Mn203＋＋H2S, and Mn204＋＋H2S. 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.