| Abstract: |
| ZrO3 and HfO3 molecules were prepared via reactions of metal monoxides with dioxygen in solid argon and were characterized using matrix isolation infrared absorption spectroscopy as well as theoretical calculations. Unlike the titanium monoxide molecule, which reacted spontaneously with dioxygen to form TiO3, the ZrO and HfO molecules reacted with dioxygen to give the ZrO3 and HfO3 molecules only under visible light irradiation. Density functional calculations predicted that both the ZrO3 and HfO3 molecules possess a closed-shell singlet ground state with a non-planar Cs geometry, in which the side-on coordinated O2 falls into the peroxide category. |
| Key words: Matrix isolation, Transition metal oxide, Dioxygen complex, Infrared spectrum |
| FundProject: |
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| Formation and Characterization of ZrO3 and HfO3 Molecules in Solid Argon |
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龚昱, 周鸣飞 *
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复旦大学化学系，上海市分子催化和功能材料重点实验室，上海200433
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| 摘要: |
| 利用低温基质隔离红外光谱技术结合量子化学计算，研究了ZrO3与HfO3的结构以及相关的生成机理. 氩基质中，在可见光激发下ZrO与HfO和氧气反应形成ZrO3与HfO3，这与TiO和氧气通过自发反应形成TiO3的机理不同. 结果表明ZrO3和HfO3都具有单重电子基态以及非平面的Cs构型，可以看作金属一氧化物二价正离子与过氧配体形成的络合物. |
| 关键词: 基质隔离，过渡金属氧化物，双氧配合物，红外光谱 |
| DOI：10.1088/1674-0068/22/02/113-118 |
| 分类号: |
