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. 2009 Apr 30;113(17):4990-5. doi: 10.1021/jp900974w.
Transition-metal dioxide anions RhO(2)(-), IrO(2)(-), PtO(2)(-), and AuO(2)(-) were produced from cocondensation of laser-ablated metal atoms and electrons with dioxygen in excess argon at 6 K. Photosensitive absorptions were assigned to the antisymmetric stretching vibration (nu(3)) of the metal dioxide anions from isotopic shifts and splittings as well as theoretical frequency calculations. On the basis of the observed nu(3) vibrational frequencies for M(16)O(2) and M(18)O(2), the anions are estimated to be linear or near linear. Density functional calculations at the DFT/B3LYP level predicted that the third-row transition-metal dioxide anions IrO(2)(-), PtO(2)(-), and AuO(2)(-) have singlet, doublet, and triplet ground states with linear structures, while the RhO(2)(-) anion was predicted to have a slightly bent geometry.
通过在6K的过量氩气中，将激光烧蚀的金属原子和电子与氧气共冷凝，制备出了过渡金属二氧化物阴离子RhO₂⁻、IrO₂⁻、PtO₂⁻和AuO₂⁻。通过同位素位移和分裂以及理论频率计算，将光敏吸收归因于金属二氧化物阴离子的反对称伸缩振动（ν₃）。根据观察到的M¹⁶O₂和M¹⁸O₂的ν₃振动频率，估计这些阴离子为线性或接近线性。在DFT/B3LYP水平上的密度泛函计算预测，第三行过渡金属二氧化物阴离子IrO₂⁻、PtO₂⁻和AuO₂⁻具有线性结构的单重态、双重态和三重态基态，而RhO₂⁻阴离子预计具有稍微弯曲的几何形状。
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