Mayhall Nicholas J, Rothgeb David W, Hossain Ekram, Raghavachari Krishnan, Jarrold Caroline Chick
Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, Indiana 47405, USA.
J Chem Phys. 2009 Mar 28;130(12):124313. doi: 10.1063/1.3100782.
The anion photoelectron spectra of MoWO(y)(-) (y=2-5) and density functional theory (DFT) calculations on MoWO(y)(-) and MoWO(y) are reported and compared to previous comparable studies on Mo(2)O(y)(-)/Mo(2)O(y) and W(2)O(y)(-)/W(2)O(y). The property governing the structure of the lowest energy MoWO(y) anion and neutral clusters is the stronger W-O bond relative to the Mo-O bond, which results in the stabilization of structures in which the Mo center is in a much lower oxidation state than the W center. Anion PE spectra show a much larger change in structure between anion and neutral states than what was observed in the pure Mo(2)O(y)(-) and W(2)O(y)(-) spectra. DFT calculations show increased single-metal localization of spin with respect to the pure metal oxide clusters.
报道了MoWO(y)(-)（y = 2 - 5）的阴离子光电子能谱以及对MoWO(y)(-)和MoWO(y)的密度泛函理论（DFT）计算，并与之前对Mo(2)O(y)(-)/Mo(2)O(y)和W(2)O(y)(-)/W(2)O(y)的类似研究进行了比较。决定最低能量的MoWO(y)阴离子和中性团簇结构的性质是相对于Mo - O键而言更强的W - O键，这导致了Mo中心氧化态远低于W中心的结构的稳定。阴离子光电子能谱显示，与纯Mo(2)O(y)(-)和W(2)O(y)(-)光谱相比，阴离子态和中性态之间的结构变化要大得多。DFT计算表明，相对于纯金属氧化物团簇，自旋的单金属局域化增加。
