Shin D N, Matsuda Y, Bernstein E R
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA.
J Chem Phys. 2004 Mar 1;120(9):4157-64. doi: 10.1063/1.1643733.
Neutral clusters of iron oxide are created by laser ablation of iron metal and subsequent reaction of the gas phase metal atoms, ions, clusters, etc., with an O2/He mixture. The FemOn clusters are cooled in a supersonic expansion and detected and identified in a time-of-flight mass spectrometer following laser ionization at 118 nm (10.5 eV), 193 nm (6.4 eV), or 355 nm (3.53 eV) photons. With 118 nm radiation, the neutral clusters do not fragment because single photon absorption is sufficient to ionize all the clusters and the energy/pulse is approximately 1 microJ. Comparison of the mass spectra obtained at 118 nm ionization (single photon) with those obtained at 193 nm and 355 nm ionization (through multiphoton processes), with regard to intensities and linewidths, leads to an understanding of the multiphoton neutral cluster fragmentation pathways. The multiphoton fragmentation mechanism for neutral iron oxide clusters during the ionization process that seems most consistent with all the data is the loss of one or two oxygen atoms. In all instances of ionization by laser photons, the most intense features are of the forms FemOm+, FemO(m+1)+, and FemO(m+2)+, and this strongly suggests that, for a given m, the most prevalent neutral clusters are of the forms FemOm, FemO(m+1), and FemO(m+2). As the value of m increases, the more oxygen rich neutral clusters appear to increase in stability.
通过对铁金属进行激光烧蚀,并使气相金属原子、离子、团簇等与O₂/He混合物发生后续反应,从而生成中性氧化铁团簇。FemOn团簇在超声速膨胀中冷却,并在118 nm(10.5 eV)、193 nm(6.4 eV)或355 nm(3.53 eV)光子进行激光电离后,在飞行时间质谱仪中进行检测和识别。使用118 nm辐射时,中性团簇不会发生碎片化,因为单光子吸收足以使所有团簇电离,且能量/脉冲约为1微焦。将118 nm电离(单光子)时获得的质谱与193 nm和355 nm电离(通过多光子过程)时获得的质谱在强度和线宽方面进行比较,有助于理解多光子中性团簇的碎片化途径。在电离过程中,中性氧化铁团簇的多光子碎片化机制似乎与所有数据最为一致的是失去一个或两个氧原子。在所有激光光子电离的情况下,最强的特征形式为FemOm⁺、FemO(m + 1)⁺和FemO(m + 2)⁺,这强烈表明,对于给定的m,最普遍的中性团簇形式为FemOm、FemO(m + 1)和FemO(m + 2)。随着m值的增加,富氧中性团簇的稳定性似乎会增加。