Reider A M, Szalay M, Reichegger J, Barabás J, Schmidt M, Kappe M, Höltzl T, Scheier P, Lushchikova O V
Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, Innsbruck 6020, Austria.
HUN-REN-BME Computation Driven Chemistry Research Group, Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Muegyetem rkp. 3, Budapest 1111, Hungary.
Phys Chem Chem Phys. 2024 Jul 31;26(30):20355-20364. doi: 10.1039/d4cp01797h.
Photofragmentation spectroscopy, combined with quantum chemical computations, was employed to investigate the position of the asymmetric CO stretch in cold, He-tagged Cu[CO] ( = 1-10) and Cu[CO][HO] ( = 1-7) complexes. A blue shift in the band position was observed compared to the free CO molecule for Cu[CO] complexes. Furthermore, this shift was found to exhibit a notable dependence on cluster size, progressively redshifting with increasing cluster size. The computations revealed that the CO binding energy is the highest for Cu and continuously decreases with increasing cluster size. This dependency could be explained by highlighting the role of polarization in electronic structure, according to energy decomposition analysis. The introduction of water to this complex amplified the redshift of the asymmetric stretch, showing a similar dependency on the cluster size as observed for Cu[CO] complexes.
采用光解离光谱结合量子化学计算方法，研究了冷态下He标记的Cu[CO]（n = 1 - 10）和Cu[CO][H₂O]（n = 1 - 7）配合物中不对称CO伸缩振动的位置。与游离CO分子相比，观察到Cu[CO]配合物的谱带位置发生蓝移。此外，发现这种位移对团簇尺寸有显著依赖性，随着团簇尺寸的增加逐渐发生红移。计算结果表明，Cu的CO结合能最高，并随着团簇尺寸的增加而持续降低。根据能量分解分析，这种依赖性可以通过强调极化在电子结构中的作用来解释。向该配合物中引入水会放大不对称伸缩振动的红移，显示出与Cu[CO]配合物类似的对团簇尺寸的依赖性。
