【摘要】 本实验采集了Cu（CO）₃^-在700～1100 nm范围内的光电子影像.通过高分辨光电子能谱的分析,精确测定了Cu（CO）₃(ν₂≈367 cm^-1)和Cu（CO）₃^-(ν₂≈408 cm^-1)的Cu-C对称伸缩频率以及Cu（CO）₃的电子亲合能（1.03±0.01 eV）.结合量子化学计算和价键分析表明,在Cu（CO）₃^-和Cu（CO）₃中,Cu和Cu^-与CO配位成键时发生4s-4p轨道杂化,并向CO的π^*反键轨道给予电子,形成反馈π键;电子贴附到Cu（CO）₃增强了Cu与CO之间配位,使Cu（CO）₃^-更加稳定;Cu和Cu^-与CO之间的相互作用主要是静电和轨道相互作用.更多还原

【Abstract】 Photoelectron velocity map images of Cu（CO）₃^-have been experimentally recorded in the 700-1100 nm range.The infrared-inactive Cu-C symmetric stretching modes for Cu（CO）₃(ν₂≈367 cm^-1) and Cu（CO）₃^-(ν₂≈408 cm^-1),as well as the electron affinity（1.03±0.01 eV） of Cu（CO）₃,are accurately determined from high resolution photoelectron spectra.In combination with quantum chemical calculations and bonding analyses,the coordination bonds in both Cu（CO）₃^- and Cu（CO）₃ are found to be due to back-donation π bonding type,formed via electron promotion from Cu’s 4s orbital to the 4p orbital,which is consequently donated to the unoccupied anti-bonding π^* orbitals of the carbonyl groups.The attachment of an additional electron to Cu（CO）₃ strengthens the Cu-CO coordination,making Cu（CO）₃^- more stable.The intramolecular interactions between the Cu/Cu^-and carbonyl groups are found to be primarily governed by electrostatic forces and orbital interactions.更多还原