Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, Brazil.
J Phys Chem A. 2012 Mar 8;116(9):2244-60. doi: 10.1021/jp208881g. Epub 2012 Feb 27.
The S 1s X-ray absorption near edge structure (XANES) and X-ray photoelectron spectra (XPS) of the neutral complexes [SbL(dmit)] (L = Br or I; dmit =1,3-dithiole-2-thione-4,5-dithiolate) have been measured using tunable synchrotron radiation. The valence shell electronic excitation by ultraviolet-visible (UV-vis) spectroscopy and the infrared vibrational spectra are presented and analyzed. The UV-vis results lead to an assignment of bands at 400 nm as π(Sm) → π*(C═S), where S(m) is the thiolate sulfur. The corresponding S 1s → π*(C═S) transition was identified at 2468.3 eV. Ab initio calculations, within the improved virtual orbital (IVO) method, carried out with the GSCF3 program, were applied to establish a complete and accurate spectral assignment. It has been the first attempt to apply such methodology for dmit coordination compounds, and very consistent results were obtained.
已使用可调谐同步辐射测量了中性配合物[SbL(dmit)]（L = Br 或 I；dmit = 1,3-二硫代-2-硫酮-4,5-二硫醇ate）的 S 1s X 射线吸收近边缘结构（XANES）和 X 射线光电子能谱（XPS）。呈现并分析了价壳层电子激发的紫外可见（UV-vis）光谱和红外振动光谱。UV-vis 结果表明，在 400nm 处的带归因于π(Sm)→π*(C═S)，其中 Sm 是硫醇硫。相应的 S 1s→π*(C═S)跃迁在 2468.3 eV 处被识别。使用 GSCF3 程序在改进的虚拟轨道 (IVO) 方法内进行的从头计算适用于建立完整且准确的光谱分配。这是首次尝试将这种方法应用于 dmit 配合物，并且得到了非常一致的结果。
