Examination of the bonding in binary transiton-metal monophosphides MP (M = Cr, Mn, Fe, Co) by x-ray photoelectron spectroscopy
Examination of the bonding in binary transiton-metal monophosphides MP (M = Cr, Mn, Fe, Co) by x-ray photoelectron spectroscopy
复制标题
DOI：
10.1021/ic051004d
复制
发表时间：
2005-11-28
影响因子：
4.6
通讯作者：
Mar, A
中科院分区：
文献类型：
--
作者：
Grosvenor, AP;Wik, SD;Mar, A
用X射线光电子能谱研究了二元过渡金属单磷化物CrP、MnP、FeP和CoP。磷2 P（3/2）芯线结合能相对于元素磷的移动表明，从CrP到CoP，金属-磷键的离子性程度降低。金属2 p（3/2）芯线结合能仅略有不同，并显示出与元素金属相似的线形，重申了这些过渡金属磷分子具有相当大的金属特性的概念。卫星结构中观察到的Co 2 P（3/2）的X射线光电子能谱的Co金属和CoP的检查反射电子能量损失谱，并已被归因于等离子体损失，而不是最终状态的影响，如先前所建议的。过渡金属磷化物的价带谱与从能带结构计算确定的态分布密度吻合得很好。从拟合的价带谱中提取了不同电子态的电子布居，这些证实了强M-P和弱P-P成键相互作用的存在。由P2p芯线谱和拟合的价带谱确定的原子电荷支持这些磷化物的近似公式M1+P1-。
The binary transition-metal monophosphides CrP, MnP, FeP, and CoP have been studied with X-ray photoelectron spectroscopy. The shifts in phosphorus 2P(3/2) Core line binding energies relative to that of elemental phosphorus indicated that the degree of ionicity of the metal-phosphorus bond decreases on progressing from CrP to CoP. The metal 2p(3/2) core line binding energies differ only slightly and show similar line shapes to those of the elemental metals, reaffirming the notion that these transition-metal phosphicles have considerable metallic character. The satellite structure observed in the Co 2P(3/2) X-ray photoelectron spectra of Co metal and CoP was examined by reflection electron energy loss spectroscopy and has been attributed to plasmon loss, not final state effects as has been previously suggested. Valence-band spectra of the transition-metal phosphides agree well with the density of states profiles determined from band structure calculations. The electron populations of the different electronic states were extracted from the fitted valence-band spectra, and these confirm the presence of strong M-P and weak P-P bonding interactions. Atomic charges determined from the P 2p core line spectra and the fitted valence-band spectra support the approximate formulation M1+P1- for these phosphides.