Reactions in Clusters as Studied by Laser Ablation-Molecular Beam Method

激光烧蚀-分子束法研究团簇反应

• 批准号: 04640471
• 负责人: SATO Hiroyasu
• 金额: $ 1.28万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640471/
• 关键词: Laser; Ablation; Moleular Beam; Clusters; Reactions in Clusters; Metal Ions; Mixed Clusters; レーザーアブレーション

In the laser ablation-molccular beam (LAMB) method developed by the present author's group, pulsed laser light jis focused on a metal surface. Metal ions (M^+) laser-ablated from the metal surface are allowed to react with molecules or clusters in a molecular beam injected nearby. Product ions are detected by a quadrupole mass spectrometer.The LAMB method is used to study reactions of metal ions with binary clusters like ammonia-methanol mixed clusters. Resulting mixed-ligand metal complex ions M^+ (NH_3) _m (CH_3OH) _n manifest a peculiar magic number-like behavior which is metal-dependent. For example, when observed relative abundances of mixed-ligand complexes M^+(NH_3)_m(CH_3OH)_n for M=Mg and Mn are plotted against m and n, the most prominent features in these distributions are the preponderance of ions with a certain number of ammonia constituents. For examle, ions with m=3 have largest abundances through the series of n=1, and those with n=2. Such a feature was found to persist through a broad range of ammonia/cethanol mixing ratio (from 600 Torr/10 Torr to 600 Torr/60 Torr). Such features indicate, without doubt, that ammmonia is directly coordinated to metal ions in these mixed-ligand complex ions. The values of m at the maxima must correspond to the number of ammonia ligands in the first coordination sphere. For examle, three ammonia molecules are bound directly to Mg^+ and Mn^+. Methanol and other ammonia molecules are bound to these three ammonia ligands. Once the first coordination sphere is comploted by three ammonia molecules, one or two methanol molecule (s) are bound to them more strongly than the fourth ammonia molecule. Such maxima of metal complex ions appeared at m=2 for the case M=Al.In summry, preferential coordination of ammonia ligands are found and their coordination number in the first coordination sphere is determined.

激光烧蚀-分子束（LAMB）法是将脉冲激光聚焦在金属表面上。从金属表面激光烧蚀的金属离子（M^+）被允许与附近注入的分子束中的分子或簇反应。用四极质谱仪检测产物离子，用LAMB方法研究了氨-甲醇混合团簇等二元团簇与金属离子的反应。所得混合配体金属配合物离子M^+（NH_3）_m（CH_3OH）_n表现出与金属相关的奇特幻数状行为。例如，当观察到的混合配体络合物M^+（NH_3）_m（CH_3OH）_n（M=Mg和Mn）的相对丰度相对于m和n作图时，这些分布中最显著的特征是具有一定数量氨组分的离子占优势。例如，m=3的离子在n=1和n=2的系列中具有最大丰度。发现这种特征在氨/乙醇混合比的宽范围内（从600托/10托到600托/60托）持续存在。这些特征表明，毫无疑问，氨是直接配位的金属离子在这些混合配体络合物离子。m在最大值处的值必须对应于第一配位层中氨配体的数目。例如，三个氨分子直接与Mg^+和Mn^+结合。甲醇和其他氨分子与这三个氨配体结合。一旦第一配位球被三个氨分子络合，则一个或两个甲醇分子比第四个氨分子更强地与它们结合。当M=Al时，配位离子的最大值出现在m=2处。总之，氨配体的优先配位被发现，并确定了它们在第一配位层的配位数。

项目成果

H.Sato et al.: "Photodissociation of Multilayered Trimethylaluminum Adsorbed on a Cryogenic Substrate:A Time-of-Flight Mass-Spectrometric Study" Applied Organometallic Chemistry. 7. 303-309 (1993)

H.Sato 等人：“低温基质上吸附的多层三甲基铝的光解离：飞行时间质谱研究”应用有机金属化学。

M.Kobayashi and H.Sato: "Preparation jof Nometallic Silver Clusters in Aquecous Solutions Using UV Lasers" Chemistry Letters. 10. 1659-1662 (1993)

M.Kobayashi 和 H.Sato：“使用紫外激光在水溶液中制备非金属银簇”化学快报。

A.Sato, Y.Tanaka, M.Tsunekawa, M.Kobayashi and H.Sato: "Laser Photodissociation of Trimethylgallium in the Gas Phase and on a Quartz Substrate As Studied by Multiphoton Ionization-Time of Flight Mass Spectroscopy" Journal of Physical Chemistry. 97 (32). 8

A.Sato、Y.Tanaka、M.Tsunekawa、M.Kobayashi 和 H.Sato：“通过多光子电离飞行时间质谱研究三甲基镓在气相中和石英基底上的激光光解离”物理化学杂志

M.Kobayashi, A.Sato, Y.Tanaka, H.Shinohara and H.Sato: "Photodissociation of Multilayred Trimethylaluminum Adsorbed on a Cryogenic Substrate : A Time-of-Flight Mass-Spectrometric Study" Applied Organometallic Chemistry. 7(5). 303-309 (1993)

M.Kobayashi、A.Sato、Y.Tanaka、H.Shinohara 和 H.Sato：“低温基质上吸附的多层三甲基铝的光解离：飞行时间质谱研究”应用有机金属化学。

M.Kobayashi: "Photodissociation of Multilayered Trimethylaluminum Adsorbed on a Cyrogenic Substrate" Applied Organometallic Chemistry. 7. (1993)

M.Kobayashi：“吸附在低温基质上的多层三甲基铝的光解离”应用有机金属化学。