Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.
J Chem Phys. 2011 Sep 14;135(10):104317. doi: 10.1063/1.3634011.
A study combining anion photoelectron spectroscopy and density functional theory calculations on the transition metal suboxide series, Nb(2)O(y)(-) (y = 2-5), is described. Photoelectron spectra of the clusters are obtained, and Franck-Condon simulations using calculated anion and neutral structures and frequencies are used to evaluate the calculations and assign transitions observed in the spectra. The spectra, several of which exhibit partially resolved vibrational structure, show an increase in electron affinity with increasing cluster oxidation state. Hole-burning experiments suggest that the photoelectron spectra of both Nb(2)O(2)(-) and Nb(2)O(3)(-) have contributions from more than one structural isomer. Reasonable agreement between experiment and computational results is found among all oxides.
描述了一项结合阴离子光电电子能谱和密度泛函理论计算的过渡金属亚氧化物系列 Nb(2)O(y)(-)（y = 2-5）的研究。获得了团簇的光电电子能谱，并使用计算得到的阴离子和中性结构和频率进行 Franck-Condon 模拟，以评估计算并分配在光谱中观察到的跃迁。这些光谱中的几个显示出部分分辨的振动结构，表明随着团簇氧化态的增加电子亲和力增加。空穴烧蚀实验表明，Nb(2)O(2)(-)和 Nb(2)O(3)(-)的光电电子能谱都有不止一种结构异构体的贡献。所有氧化物的实验结果和计算结果之间都存在合理的一致性。
