Molek K S, Reed Z D, Ricks A M, Duncan M A
Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556, USA.
J Phys Chem A. 2007 Aug 23;111(33):8080-9. doi: 10.1021/jp073789+. Epub 2007 Aug 1.
Chromium oxide cluster cations, Cr(n)O(m)+, are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. The mass spectrum exhibits a limited number of stoichiometries for each value of n, where m > n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic output of a Nd:YAG laser. At either wavelength, multiphoton absorption is required to dissociate these clusters, which is consistent with their expected strong bonding. Cluster dissociation occurs via elimination of molecular oxygen, or by fission processes producing stable cation species and/or eliminating stable neutrals such as CrO3, Cr(2)O(5), or Cr(4)O(10). Specific cation clusters identified to be stable because they are produced repeatedly in the decomposition of larger clusters include Cr(2)O(4)+, Cr(3)O(6)+, Cr(3)O(7)+, Cr(4)O(9)+, and Cr(4)O(10)+.
氧化铬簇阳离子Cr(n)O(m)+通过脉冲喷嘴簇源中的激光汽化产生,并采用飞行时间质谱进行检测。对于每个n值(其中m > n),质谱显示出有限数量的化学计量比。使用Nd:YAG激光的二次谐波输出(532 nm)或三次谐波输出(355 nm)对簇阳离子进行质量选择和光解离。在任一波长下,都需要多光子吸收来解离这些簇,这与其预期的强键合一致。簇解离通过消除分子氧或通过裂变过程产生稳定的阳离子物种和/或消除稳定的中性物质(如CrO3、Cr(2)O(5)或Cr(4)O(10))来发生。被确定为稳定的特定阳离子簇,因为它们在较大簇的分解过程中反复产生,包括Cr(2)O(4)+、Cr(3)O(6)+、Cr(3)O(7)+、Cr(4)O(9)+和Cr(4)O(10)+。