Extensive DFT calculations are performed to optimize the geometric structures of O-rich tungsten oxide clusters, to simulate the PES spectra, and to analyze the chemical bonding. The ground-state structure of W4O14^- ...Extensive DFT calculations are performed to optimize the geometric structures of O-rich tungsten oxide clusters, to simulate the PES spectra, and to analyze the chemical bonding. The ground-state structure of W4O14^- is best considered as W4O12（O2^-）, containing a side-on bound superoxide ligand. The current study indicates that the extra electron in W4O12^- is capable of activating dioxygen by non-dissociative electron transfer （W 5d → O2 π^＊）, and the anionic clusters can be viewed as models for reduced defect sites on tungsten oxide surfaces for the chemisorption of O2.展开更多
基金the National Natural Science Foundation of China (20641004, 20771026 and 20773024)the Natural Science Foundation of Fujian Province (No. 2008J0151)
文摘Extensive DFT calculations are performed to optimize the geometric structures of O-rich tungsten oxide clusters, to simulate the PES spectra, and to analyze the chemical bonding. The ground-state structure of W4O14^- is best considered as W4O12（O2^-）, containing a side-on bound superoxide ligand. The current study indicates that the extra electron in W4O12^- is capable of activating dioxygen by non-dissociative electron transfer （W 5d → O2 π^＊）, and the anionic clusters can be viewed as models for reduced defect sites on tungsten oxide surfaces for the chemisorption of O2.
