Petric Marko, Bohinc Rok, Bučar Klemen, Žitnik Matjaž, Szlachetko Jakub, Kavčič Matjaž
†J. Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia.
‡Jozef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia.
Anal Chem. 2015 Jun 2;87(11):5632-9. doi: 10.1021/acs.analchem.5b00782. Epub 2015 May 14.
An experimental and theoretical study of phosphorus electronic structure based on high energy resolution X-ray emission spectroscopy was performed. The Kα and Kβ emission spectra of several phosphorus compounds were recorded using monochromatic synchrotron radiation and megaelectronvolt (MeV) proton beam for target excitation. Measured spectra are compared to the results of ab initio quantum chemical calculations based on density functional theory (DFT). Clear correlation between energy position of the Kα emission line and the phosphorus formal oxidation state as well as DFT-calculated number of valence electrons is obtained; measured energy shifts are reproduced by the calculations. Chemical sensitivity is increased further by looking at the Kβ emission spectra probing directly the structure of occupied molecular orbitals. Energies and relative intensities of main components are given together with the calculated average atomic character of the corresponding molecular orbitals involved in transitions.
开展了一项基于高能分辨率X射线发射光谱的磷电子结构实验与理论研究。使用单色同步辐射和兆电子伏特（MeV）质子束激发靶材，记录了几种磷化合物的Kα和Kβ发射光谱。将测量光谱与基于密度泛函理论（DFT）的从头算量子化学计算结果进行了比较。获得了Kα发射线的能量位置与磷的形式氧化态以及DFT计算的价电子数之间的明确相关性；计算结果再现了测量到的能量位移。通过观察直接探测占据分子轨道结构的Kβ发射光谱，进一步提高了化学灵敏度。给出了主要成分的能量和相对强度，以及参与跃迁的相应分子轨道的计算平均原子特征。
