Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.
J Phys Chem A. 2010 Oct 28;114(42):11312-21. doi: 10.1021/jp1044223.
The vibrationally resolved anion photoelectron (PE) spectra of MoVO(y)(-) (y = 2 - 5) metal suboxide clusters are presented and analyzed in the context of density functional theory (DFT) calculations. The electronically congested spectra reflect an increase in cluster electron affinity with increasing oxidation state. Ion beam hole-burning results reveal the features in the PE spectra of MoVO(2)(-) and MoVO(4)(-) are a result of only one anion isomer, while at least two isomers contribute to electronic structure observed in the PE spectrum of MoVO(3)(-). Spectral features of the binary systems are compared to their pure analogs, Mo(2)O(y) and V(2)O(y). An attempt to characterize the anion and neutral electronic and molecular structures is made by comparison with results from DFT calculations. However, reconciliation between the cluster spectra and the calculated spectroscopic parameters is not as straightforward as in previous studies on similar systems (Yoder, B. L.; Maze, J. T.; Raghavachari, K.; Jarrold, C. C. J. Chem. Phys. 2005, 122, 094313 and Mayhall, N. J.; Rothgeb, D. W.; Hossain, E.; Raghavachari, K.; Jarrold, C. C. J. Chem. Phys. 2009, 130, 124313).
MoVO(y)(-)（y=2-5）金属亚氧化物团簇的振动分辨阴离子光电离（PE）谱，并结合密度泛函理论（DFT）计算进行了分析。电子拥挤的光谱反映了随着氧化态的增加，团簇电子亲和力的增加。离子束空穴烧蚀结果表明，MoVO(2)(-)和 MoVO(4)(-)的 PE 光谱中的特征仅源于一种阴离子异构体，而 MoVO(3)(-)的 PE 光谱中观察到的电子结构则至少有两种异构体。二元体系的光谱特征与它们的纯类似物 Mo(2)O(y)和 V(2)O(y)进行了比较。通过与 DFT 计算结果的比较，尝试对阴离子和中性电子及分子结构进行了特征化。然而，与类似体系（Yoder，B. L.；Maze，J. T.；Raghavachari，K.；Jarrold，C. C. J. Chem. Phys. 2005，122，094313 和 Mayhall，N. J.；Rothgeb，D. W.；Hossain，E.；Raghavachari，K.；Jarrold，C. C. J. Chem. Phys. 2009，130，124313）之前的研究相比，簇光谱与计算光谱参数之间的调和并不那么直接。
