Jiang Ling, Teng Yun-Lei, Xu Qiang
National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka, Japan.
J Phys Chem A. 2006 Jun 8;110(22):7092-6. doi: 10.1021/jp0614852.
Reactions of laser-ablated zinc and cadmium atoms with carbon monoxide molecules in solid neon have been investigated using matrix-isolation infrared spectroscopy. Based on the isotopic substitution, absorptions at 1852.2, 1901.9, 1945.9, and 1995.2 cm(-1) are assigned to the C-O stretching vibrations of the ZnCO, Zn(CO)(2), and Zn(CO)(3) molecules. Absorptions at 1735.8, 1961.3, and 2035.7 cm(-1) are assigned to the C-O stretching vibrations of the CdCO(-) and Cd(CO)(2) molecules. In contrast with the previous argon experiments, more species and more valuable information about the reaction of zinc and cadmium atoms with CO have been obtained in solid neon. Density functional theory calculations have been performed on these zinc and cadmium carbonyls. The agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts substantiates the identification of these carbonyls from the matrix infrared spectrum. The present experiments also reveal that zinc is more reactive with CO than cadmium.
利用基质隔离红外光谱研究了在固体氖中激光烧蚀的锌原子和镉原子与一氧化碳分子的反应。基于同位素取代，1852.2、1901.9、1945.9和1995.2 cm⁻¹处的吸收峰被归属为ZnCO、Zn(CO)₂和Zn(CO)₃分子的C - O伸缩振动。1735.8、1961.3和2035.7 cm⁻¹处的吸收峰被归属为CdCO⁻和Cd(CO)₂分子的C - O伸缩振动。与之前在氩气中的实验相比，在固体氖中获得了更多关于锌和镉原子与CO反应的物种及更有价值的信息。对这些锌和镉的羰基化合物进行了密度泛函理论计算。实验和计算得到的振动频率、相对吸收强度及同位素位移之间的一致性证实了从基质红外光谱中对这些羰基化合物的鉴定。目前的实验还表明锌与CO的反应性比镉更强。
