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氨分子簇与氦液滴中嵌入的 C60 聚集体的离子-分子反应。

Ion-molecule reactions of ammonia clusters with C60 aggregates embedded in helium droplets.

机构信息

Institut für Ionenphysik und Angewandte Physik and Center for Molecular Biosciences Innsbruck, Leopold Franzens Universität, Technikerstr. 25, A-6020 Innsbruck, Austria.

出版信息

Phys Chem Chem Phys. 2011 Jan 21;13(3):1092-8. doi: 10.1039/c0cp01268h. Epub 2010 Nov 12.

DOI:10.1039/c0cp01268h
PMID:21072422
Abstract

Helium nanodroplets are co-doped with C(60) and ammonia. Mass spectra obtained by electron ionization reveal cations containing ammonia clusters complexed with up to four C(60) units. The high mass resolution of Δm/m≈ 1/6000 makes it possible to separate the contributions of protonated, unprotonated and dehydrogenated ammonia. C(60) aggregates suppress the proton-transfer reaction which usually favors the appearance of protonated ammonia cluster ions. Unprotonated C(x)(NH(3))(n)(+) ions (x = 60, 120, 180) exceed the abundance of the corresponding protonated ions if n < 5; for larger values of n the abundances of C(60)(NH(3))(n)(+) and C(60)(NH)(n-1)NH(4)(+) become about equal. Dehydrogenated C(60)NH(2)(+) ions are relatively abundant; their formation is attributed to a transient doubly charged C(60)-ammonia complex which forms either by an Auger process or by Penning ionization following charge transfer between the primary He(+) ion and C(60). The abundance of C(x)NH(3)(+) and C(x)NH(4)(+) ions (x = 120 or 180) is one to two orders of magnitude weaker than the abundance of ions containing one or two additional ammonia molecules. However, a model involving evaporation of NH(3) or NH(4) from the presumably weakly bound C(x)NH(3)(+) and C(x)NH(4)(+) ions is at odds with the lack of enhancement in the abundance of C(120)(+) and C(180)(+). Mass spectra of C(60) dimers complexed with water complement a previous study of C(60)(H(2)O)(n)(+) recorded at much lower mass resolution.

摘要

氦纳米液滴共掺杂了 C(60)和氨。电子电离得到的质谱显示,氨簇合物与多达四个 C(60)单元形成了阳离子。高质量分辨率Δm/m≈1/6000 使得分离质子化、非质子化和脱氢氨的贡献成为可能。C(60)聚集体抑制了通常有利于质子化氨簇离子出现的质子转移反应。如果 n < 5,则未质子化的 C(x)(NH(3))(n)(+)离子(x = 60、120、180)的丰度超过相应的质子化离子;对于较大的 n 值,C(60)(NH(3))(n)(+)和 C(60)(NH)(n-1)NH(4)(+)的丰度变得大致相等。脱氢的 C(60)NH(2)(+)离子相对丰富;它们的形成归因于瞬态的双电荷 C(60)-氨络合物,该络合物可以通过俄歇过程或通过主 He(+)离子与 C(60)之间的电荷转移后的彭宁电离形成。C(x)NH(3)(+)和 C(x)NH(4)(+)离子(x = 120 或 180)的丰度比含有一个或两个额外氨分子的离子的丰度弱一到两个数量级。然而,一个涉及 NH(3)或 NH(4)从假定的弱结合 C(x)NH(3)(+)和 C(x)NH(4)(+)离子蒸发的模型与 C(120)(+)和 C(180)(+)丰度的缺乏增强相矛盾。与以前在低得多的质量分辨率下记录的 C(60)(H(2)O)(n)(+)的研究相比,C(60)二聚体与水络合物的质谱得到了补充。

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