School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Tianhe District, Guangzhou 510640, China.
Chemphyschem. 2012 Apr 10;13(5):1282-8. doi: 10.1002/cphc.201100973. Epub 2012 Feb 29.
Oxygen-rich scandium cluster anions ScO(3-5)(-) are prepared by laser ablation and allowed to react with n-butane in a fast-flow reactor. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. The ScO(3)(-) and ScO(4)(-) clusters can react with n-butane to produce ScO(3)H(-), ScO(3)H(2)(-), and ScO(4)H(-), while the more oxygen-rich cluster ScO(5)(-) is inert. The experiment suggests that unreactive cluster isomers of ScO(3)(-) and ScO(4)(-) are also present in the cluster source. Density functional theory and ab initio methods are used to calculate the structures and reaction mechanisms of the clusters. The theoretical results indicate that the unreactive and reactive cluster isomers of ScO(3,4)(-) contain peroxides (O(2)(2-)) and oxygen-centered radicals (O(.-)), respectively. The mechanisms and energetics for conversion of unreactive O(2)(2-) to reactive O(.-) species are also theoretically studied.
富氧钪团簇阴离子 ScO(3-5)(-) 通过激光烧蚀制备，并在快速流动反应器中与正丁烷反应。使用飞行时间质谱仪在反应前后检测团簇分布。ScO(3)(-) 和 ScO(4)(-) 团簇可以与正丁烷反应生成 ScO(3)H(-)、ScO(3)H(2)(-) 和 ScO(4)H(-)，而更富氧的 ScO(5)(-) 团簇则是惰性的。实验表明，ScO(3)(-) 和 ScO(4)(-) 的非反应性团簇异构体也存在于团簇源中。密度泛函理论和从头计算方法用于计算团簇的结构和反应机制。理论结果表明，ScO(3,4)(-) 的非反应性和反应性团簇异构体分别含有过氧化物 (O(2)(2-)) 和氧中心自由基 (O(.-))。还从理论上研究了将非反应性 O(2)(2-) 转化为反应性 O(.-) 物种的机制和能量学。
