(1. 广西大学 资源与冶金学院，南宁 530004；
2. 广西大学 广西高校矿物工程重点实验室，南宁 530004；
3. 广西大学 材料科学与工程学院，南宁 530004)
摘 要: 采用密度泛函理论，计算方铅矿、黄铁矿和闪锌矿的体相及表面电子性质，研究表面空间结构对这3种典型硫化矿物能带结构和电子性质的影响。结果表明：表面结构弛豫导致方铅矿(100)表面带隙变大，表面电子比体相更加活跃；而黄铁矿(100)表面带隙变窄，表面显示出一定的金属性。对3种硫化矿表面原子Mulliken电荷的分析表明，闪锌矿(110)表面和方铅矿(100)表面的电子从体相向表面层转移；而黄铁矿(100)表面的电子则从表面向体相转移。对黄铁矿体相和(100)、(210)和(110)表面具有不同配位数的铁原子的态密度分析表明，铁原子配位数的减少，导致Fe 3d电子能级升高，表面态能级变大。
关键字: 硫化矿；空间结构；密度泛函理论；电子性质；能带结构
（1. College of Resources and Metallurgy, Guangxi University, Nanning 530004, China;
2. Guangxi Colleges and Universities Key Laboratory of Minerals Engineering, Guangxi University, Nanning 530004, China;
3. School of Materials Science and Engineering, Guangxi University, Nanning 530004, China）
Abstract:The bulk and surface electronic properties of galena, pyrite and sphalerite were calculated by adopting density functional theory, and the effects of spatial structure on the band structure and electronic properties of these three typical sulphide minerals were studied. The results show that surface relaxation leads a greater band gap of PbS (100) surface compared with the bulk PbS, and the surface electrons are more reactive than the bulk electrons, while for the FeS2 (100) surface, the band gap decreases and shows a metallic characteristics. The analysis of surface Mulliken charge of these three sulphide minerals suggests that, for the PbS (100) and ZnS (110), the electrons transfer from the bulk to the surface, however, the electrons of FeS2 (100) transfer from the surface to the bulk. The DOS of bulk pyrite and surface pyrite Fe atom with different coordination number indicate that the decrease of coordination number leads to the increase of Fe 3d energy level and Tamm surface energy level.
Key words: sulfide mineral; spatial structure; density functional theory; electronic property; band structure
