Monohafnium Oxide Clusters HfOn鈥?/sup> and HfOn (n = 1鈥?): Oxygen Radicals, Superoxides, Peroxides, Diradicals, and Triradicals

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• 作者：Hua-Jin Zhai ; Wen-Jie Chen ; Shu-Juan Lin ; Xin Huang ; Lai-Sheng Wang
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：February 14, 2013
• 年：2013
• 卷：117
• 期：6
• 页码：1042-1052
• 全文大小：599K
• 年卷期：v.117,no.6(February 14, 2013)
• ISSN：1520-5215

文摘

The electronic and structural properties of monohafnium oxide clusters, HfO_n^{鈥?/sup> and HfO_n (n = 1鈥?), are investigated using anion photoelectron spectroscopy and density-functional theory at the B3LYP level. The observed ground-state adiabatic detachment energy is low for HfO鈥?/sup> (0.5 卤 0.1 eV) and HfO₂鈥?/sup> (2.125 卤 0.010 eV), roughly constant for HfO₃鈥?/sup> (3.6 卤 0.1 eV), HfO₄鈥?/sup> (3.67 卤 0.05 eV), and HfO₅鈥?/sup> (3.9 卤 0.1 eV), and substantially higher for HfO₆鈥?/sup> (4.9 卤 0.1 eV). Activated oxygen species, such as radical, superoxide, peroxide, diradical, and triradical, are identified in the HfO_n鈥?/sup> and HfO_n clusters. The Hf center is shown to be flexible to accommodate the oxygen species. The sum of formal Hf鈥揙 bond orders around the Hf center is equal to four for all of the neutral clusters studied, and five for all of the anions. The O-rich HfO_n鈥?/sup> and HfO_n (n = 3鈥?) clusters provide well-defined molecular models to understand O₂ adsorption and activation on an Hf center.}