Wang Xuefeng, Andrews Lester
Chemistry Department, University of Virginia, P.O. Box 400319, Charlottesville, Virginia 22904-4319, USA.
J Phys Chem A. 2005 May 5;109(17):3849-57. doi: 10.1021/jp050362z.
Laser-ablated zinc and cadmium atoms were mixed uniformly with H2 and O2 in excess argon or neon and with O2 in pure hydrogen or deuterium during deposition at 8 or 4 K. UV irradiation excites metal atoms to insert into O2 producing OMO molecules (M = Zn, Cd), which react further with H2 to give the metal hydroxides M(OH)2 and HMOH. The M(OH)2 molecules were identified through O-H and M-O stretching modes with appropriate HD, D2, (16,18)O2, and (18)O2 isotopic shifts. The HMOH molecules were characterized by O-H, M-H, and M-O stretching modes and an M-O-H bending mode, which were particularly strong in pure H2/D2. Analogous Zn and Cd atom reactions with H2O2 in excess argon produced the same M(OH)2 absorptions. Density functional theory and MP2 calculations reproduce the IR spectra of these molecules. The bonding of Group 12 metal dihydroxides and comparison to Group 2 dihydroxides are discussed. Although the Group 12 dihydroxide O-H stretching frequencies are lower, calculated charges show that the Group 2 dihydroxide molecules are more ionic.
在8K或4K的沉积过程中，用激光烧蚀的锌和镉原子与过量氩气或氖气中的H₂和O₂以及纯氢气或氘气中的O₂均匀混合。紫外线照射使金属原子插入O₂中生成OMO分子（M = Zn、Cd），这些分子再与H₂进一步反应生成金属氢氧化物M(OH)₂和HMOH。通过O - H和M - O伸缩模式以及适当的HD、D₂、(¹⁶,¹⁸)O₂和(¹⁸)O₂同位素位移来识别M(OH)₂分子。HMOH分子通过O - H、M - H和M - O伸缩模式以及M - O - H弯曲模式来表征，这些模式在纯H₂/D₂中尤为明显。在过量氩气中，锌和镉原子与H₂O₂发生类似反应，也产生相同的M(OH)₂吸收峰。密度泛函理论和MP2计算再现了这些分子的红外光谱。文中还讨论了第12族金属二氢氧化物的键合情况，并与第2族二氢氧化物进行了比较。尽管第12族二氢氧化物的O - H伸缩频率较低，但计算电荷表明第2族二氢氧化物分子的离子性更强。
