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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >Photoelectron spectroscopic and computational studies of the Pt@Pb101- and Pt@Pb121-/2- anions
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Photoelectron spectroscopic and computational studies of the Pt@Pb101- and Pt@Pb121-/2- anions

机译:Pt @ Pb101-和Pt @ Pb121- / 2-阴离子的光电子能谱和计算研究

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摘要

A combination of anion photoelectron spectroscopy and density functional theory calculations has elucidated the geometric and electronic structure of gas-phase endohedral Pt/Pb cage cluster anions. The anions, Pt@Pb101~ and Pt@Pb121~ were prepared from "preassembled" clusters generated from crystalline samples of K(2,2,2-crypt) 2 Pt@Pb12] that were brought into the gas phase using a unique infrared desorption/photoemission anion source. The use of crystalline [K(2,2,2-crypt)]2[Pt@Pb12] also provided access to K[Pt@Pbn]~ anions in the gas phase (i.e., the K salts of the Pt@Pbn2~ anions). Anion photoelectron spectra of Pt@Pb101~, Pt@Pb121~, and K[Pt@Pbi2]1" are presented. Extensive density functional theory calculations on Pt@Pb103 -/2-/1-/0 anc| pt@Pb122/1" provided candidate structures and anion photoelectron spectra for Pt@Pb101~ and Pt@Pb121~. Together, the calculated and measured photoelectron spectra show that Pt@Pb101~ and Pt@Pb122~/1~ endohedral complexes maintain their respective DM and slightly distorted lh symmetries in the gas phase even for the charge states with open shell character. Aside from the fullerenes, the Pt@Pb122~ endohedral complex is the only bare cluster that has been structurally characterized in the solid state, solution, and the gas phase.
机译:阴离子光电子能谱法和密度泛函理论计算相结合,阐明了气相内面Pt / Pb笼状簇阴离子的几何结构和电子结构。阴离子Pt @ Pb101〜和Pt @ Pb121〜是由K(2,2,2-crypt)2 Pt @ Pb12]晶体样品生成的“预组装”簇制备的,这些簇通过使用独特的红外光谱进入气相解吸/光发射阴离子源。晶体[K(2,2,2-crypt)] 2 [Pt @ Pb12]的使用还提供了气相中K [Pt @ Pbn]〜阴离子(即Pt @ Pbn2〜的K盐)的获取途径。阴离子)。给出了Pt @ Pb101〜,Pt @ Pb121〜和K [Pt @ Pbi2] 1“的阴离子光电子能谱。关于Pt @ Pb103-/ 2- / 1- / 0 anc | pt @ Pb122 /的广泛密度泛函理论计算1”提供了Pt @ Pb101〜和Pt @ Pb121〜的候选结构和阴离子光电子能谱。总之,计算和测量的光电子能谱显示,即使对于具有开壳特性的电荷状态,Pt @ Pb101〜和Pt @ Pb122〜/ 1〜内衬复合物在气相中也保持各自的DM和略微扭曲的lh对称性。除富勒烯外,Pt @ Pb122〜内衬复合物是唯一在结构上以固态,溶液和气相为特征的裸簇。

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  • 作者单位

    Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218;

    Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218;

    Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218;

    Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218;

    Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742;

    Center for Computational Materials Science, Naval Research Laboratory, Washington, DC 20375;

    Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218;

    Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    endohedral clusters; negative ions; mass spectrometry;

    机译:内面簇;负离子;质谱;

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