Closed-Cage Tungsten Oxide Clusters in the Gas Phase

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• 作者：D. M. David Jeba Singh ; T. Pradeep ; Krishnan Thirumoorthy ; Krishnan Balasubramanian
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：May 6, 2010
• 年：2010
• 卷：114
• 期：17
• 页码：5445-5452
• 全文大小：481K
• 年卷期：v.114,no.17(May 6, 2010)
• ISSN：1520-5215

文摘

During the course of a study on the clustering of W−Se and W−S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W−O clusters. Three distinct species, W₆O₁₉⁻, W₁₃O₂₉⁻, and W₁₄O₃₂⁻, stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W₁₃ and W₁₄ clusters were observed for the first time in the gas phase.