Zhang Qingqing, Zhao Yanying, Gong Yu, Zhou Mingfei
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, People's Republic of China.
J Phys Chem A. 2007 Oct 4;111(39):9775-80. doi: 10.1021/jp073599z. Epub 2007 Sep 7.
Dichromium oxide clusters, Cr2O2, Cr2O4, and Cr2O6, have been prepared and characterized by matrix isolation infrared spectroscopy and quantum chemical calculations. Laser-evaporated chromium atoms reacted with O2 in solid argon to form the previously characterized CrO2 molecules, which further reacted with chromium atoms to form Cr2O2 spontaneously on annealing. The Cr2O2 cluster is determined to have a chainlike CrOCrO structure. The rhombic ring isomer, which was predicted to be more stable than the CrOCrO structure, was not formed at the present experimental conditions. The Cr2O4 cluster was formed from the barrierless dimerization of the chromium dioxide molecules, which is characterized to have a planar D2h symmetry. TheCr2O6 cluster was produced under UV light irradiation. It is determined to have a singlet ground state with a nonplanar D2h symmetry.
通过基质隔离红外光谱和量子化学计算，制备并表征了二铬氧化物簇Cr₂O₂、Cr₂O₄和Cr₂O₆。激光蒸发的铬原子在固态氩中与O₂反应形成先前已表征的CrO₂分子，这些分子在退火时进一步与铬原子自发反应形成Cr₂O₂。确定Cr₂O₂簇具有链状CrOCrO结构。菱形环异构体预计比CrOCrO结构更稳定，但在当前实验条件下未形成。Cr₂O₄簇由二氧化铬分子的无障碍二聚反应形成，其特征为具有平面D₂h对称性。Cr₂O₆簇在紫外光照射下产生。确定其基态为单重态，具有非平面D₂h对称性。
