Direct Correlation between the 31P MAS NMR Response and the Electronic Structure of Some Transition Metal Phosphides

被引:54
作者
Bekaert, E. [1 ]
Bernardi, J. [2 ]
Boyanov, S. [2 ]
Monconduit, L. [2 ]
Doublet, M. -L. [2 ]
Menetrier, M. [1 ]
机构
[1] Univ Bordeaux 1, ICMCB, CNRS, F-33608 Pessac, France
[2] UMI, ENSCM, UMII, CNRS,Inst Charles Gerhardt, F-34095 Montpellier 5, France
关键词
D O I
10.1021/jp808122q
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A series of binary transition metal phosphides (Ni3P, Ni12P5, Ni2P, Ni5P4, NiP, NiP2, FeP, FeP2, FeP4, VP2, CoP) were investigated by solid state P-31 MAS NMR, leading to rather different lineshapes, shifts, relaxation times, and temperature dependences. The electronic structures of these compounds were computed using various DFT codes, based either on plane wave PAW potentials (VASP) or on all-electron basis sets in the FPLAPW formalism (Wien2K). Depending on the electronic features of the phosphide, self-interaction corrected formalisms (DFT+U or PBEO hybrid functional) were also used to reach a better description of the electronic ground state and to establish a correlation with the shape and the nature of the NMR signals. As a result of the analysis, the main categories are diamagnetic compounds (FeP4, NiP2) and metallic ones, either real (VP2) or with some electronic localization in band tails (Ni12P5, Ni2P, Ni5P4, NiP) or with spin-polarized conduction bands (CoP, FeP). FeP2 appears somewhat ambiguous, both based on the various computational results and on the NMR characteristics. Besides, FeP4 is the only compound for which very clear J couplings resulting from P-P bonds were observed.
引用
收藏
页码:20481 / 20490
页数:10
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