Investigating the Relative Stabilities and Electronic Properties of Small Zinc Oxide Clusters

详细信息    查看全文

• 作者：K. Don Dasitha Gunaratne ; Cuneyt Berkdemir ; Christopher L. Harmon ; A. W. Castleman ; Jr.
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：December 27, 2012
• 年：2012
• 卷：116
• 期：51
• 页码：12429-12437
• 全文大小：357K
• 年卷期：v.116,no.51(December 27, 2012)
• ISSN：1520-5215

文摘

We report a combined experimental and theoretical study investigating small zinc oxide clusters. A laser vaporization source and a time-of-flight (TOF) mass spectrometer are employed to produce and identify anionic clusters in the Zn_nO_m (n = 1鈥?, m = 1鈥?) size regime. The adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of Zn₃O₃^{鈥?/sup> and Zn₃O₄鈥?/sup> clusters are determined via anion photoelectron spectroscopy. We have utilized density functional theory (DFT) calculations to explore the possible geometries of neutral and anionic Zn₃O_m (m = 3鈥?) clusters, while the theoretical ADE and VDE values are compared with experimental results. The experimentally observed relative abundances among the Zn₃O_m鈥?/sup> (m = 3鈥?) clusters are investigated through calculations of the detachment energies, dissociation energies, and HOMO鈥揕UMO gaps. We find that the Zn₃O₃ cluster maintains enhanced stability compared to their oxygen-rich counterparts. Furthermore, by coupling the experimentally obtained photoelectron angular distributions of Zn₃O₃鈥?/sup> and Zn₃O₄鈥?/sup> with electronic structure calculations, the nature of the highest occupied molecular orbitals is discussed, with the goal of aiding the isolation (ligand-capped)/deposition of these building blocks.}