氟磷灰石、氯磷灰石和羟基磷灰石电子结构的第一性原理研究

发布时间：2018-10-10 06:50

【摘要】：基于密度泛函理论(DFT)的第一性原理,研究了氟磷灰石、氯磷灰石和羟基磷灰石的电子结构,讨论了不同通道离子(F-、Cl-、OH-)对磷灰石电子结构的影响。能带分析表明:氟磷灰石、氯磷灰石和羟基磷灰石均为绝缘体,其带宽分别为5.600、5.384和3.577 e V。态密度分析表明:通道离子对3种磷灰石的态密度影响较大,氟磷灰石与氯磷灰石导带部分有Ca1 3d轨道和Ca2 3d轨道的贡献;羟基磷灰石态密度导带部分仅有Ca2 3d轨道的贡献,导致Ca2还原性降低;羟基磷灰石态密度向低能级方向移动,形成新的深部价带;Cl的态密度较F的态密度向高能级方向移动,导致形成新的中部价带-12.5~14.0 e V,该价带仅由Cl 3s轨道组成。Mulliken电荷布居及键布居表明:F得电荷能力强于Cl,主要是F的2p轨道得电荷能力强于Cl的3p轨道;3种磷灰石中的O—P键布居接近且均较大,共价性较强,F—Ca与Cl—Ca布居接近,但F—Ca键长小于Cl—Ca键长,F—Ca结合作用强于Cl—Ca。
[Abstract]:Based on the first principle of density functional theory (DFT), the electronic structures of fluoroapatite, chlorapatite and hydroxyapatite were studied. The band analysis shows that fluoroapatite, chlorapatite and hydroxyapatite are insulators with a bandwidth of 5.600,5.384 and 3.577 EV, respectively. The analysis of the density of states shows that the channel ions have a great influence on the density of states of the three kinds of apatite. The contribution of Ca1 3D orbital and Ca2 3D orbital is in the conduction band of fluorapatite and chlorapatite, and the contribution of Ca2 3D orbital is the only contribution of hydroxyapatite density conduction band. As a result of the reduction of Ca2, the density of states of hydroxyapatite moved to the direction of low energy level, and the density of states of the new deep valence band Cl moved to the high energy level than the density of states of F. A new middle valence band -12.5 ~ 14.0 EV was formed. The valence band consists only of the Cl 3s orbital. Mulliken charge population and bond population show that the charge ability of Cl, is stronger than that of Cl, 's 2p orbital, which is stronger than that of Cl's 3p orbital. The O-P bond population is close and large, The covalent ratio of F-Ca is close to that of Cl-Ca, but the length of F-Ca is smaller than that of Cl-Ca. F-Ca is stronger than Cl-Ca..
【作者单位】：贵州大学矿业学院;喀斯特地区优势矿产资源高效利用国家地方联合工程实验室;贵州省非金属矿产资源综合利用重点实验室;
【基金】：贵州省高层次创新型人才培养((2015)4012)
【分类号】：O611.2

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