Co-P非晶态合金电子性质和局域结构的理论研究

根据Co P非晶态合金结构的短程有序和结构中可能存在P -P相互作用的实验事实 ,选择了单磷原子簇模型ConP(n =1～ 5 )和双磷原子簇模型ConP2 (n =1～ 4 ) ,用密度泛函理论方法对其进行计算 .结果表明 ,在单磷Co2 P( 2 ) 、Co3 P( 1) 及Co4P( 2 ) 模型体系中 ,Co原子供给P原子电子 ,与电负性规则一致 ,同时Co和P之间具较强化学作用 ,可以形成稳定的原子簇 ;而在双磷和单磷原子簇Co5P( 1) 模型体系中 ,形成的原子簇不稳定 ,采用单磷Co2 P( 2 ) 、Co3 P( 1) 及Co4P( 2 ) 模型能较好地反映Co P非晶态合金的结构特点 .     

非晶态合金Fe80P20局域结构和性质的量子化学研究

利用原子簇模型Fe_4P简化了非晶态合金Fe_(80)P_(20)的局域结构,设计了四方锥、三角双锥、四面体及平面五边形等十几种构型,对其二、四重态分别进行密度泛函(DFT)优化计算,经过频率验证,获得五种稳定构型。从所得优化构型的键长和键级,可以发现原子簇Fe4P较好地反映了非晶态合金Fe_(80)P_(20)的局域结构。考察了各构型间的过渡转化情况,发现二重态构型的稳定性要好于四重态。分析各构型的能量、成键及电子转移情况,发现与P原子成键的Fe原子个数对这些性质影响较为明显。与P原子成键的Fe原子个数越多,体系的能量就越低,越容易存在；P原子的得电子能力随着与其成键Fe原子个数增多而减少,甚至会将失去自身电子转移到金属原子上。同时通过3d轨道布居数,讨论了原子簇的空穴数及磁学性质。     

MgnPm团簇的几何结构，电子性质和稳定性的密度泛函研究

本文运用密度泛函理论在B3LYP6-311G水平上对MgnPm(n=1～2,m=1～8)团簇的几何构型,稳定性以及电子性质进行了较详细的计算研究.在优化所得的MgnPm(n=1～2,m=1～8)基态结构中,n m≥4时,团簇易形成五元环和四元环型结构.在得到的基态结构的基础上,我们对最低能量结构的二阶能量差分和能隙进行了计算,结果表明MgP4,MgP6,Mg2P2以及Mg2P4具有较高的相对稳定性.在对自然电子组态和电荷布居的进一步分析发现,P原子获得电荷的多少取决于P,Mg原子之间的距离的大小.     

Co_mAl_n(m+n≤6)团簇的结构和磁性理论研究

采用密度泛函理论中的广义梯度近似(DFT-GGA)对ComAln(m+n 6)合金团簇进行了系统的几何、电子结构和磁性质研究.研究结果发现ComAln(m+n 6)团簇最稳定结构倾向于形成Co—Al成键数最多的构型,其中的Co—Al二元合金团簇的最稳定结构类似于纯钴团簇.随着Al原子数的增多,团簇的平均磁矩呈线性降低趋势.ComAl(m=2—5)团簇的总磁矩均比Com+1团簇的小4μB,与实验上对较大CoNAlM团簇的磁性检测结果获得了很好地符合.ComAln团簇磁性的降低主要归因于非磁性Al元素的掺入以及Al掺杂后Co原子的整体自旋极化减弱.     

铍原子里德堡能级的计算(英文)

依据最弱受约束电子势模型理论,计算了铍原子1s~22sns~1S_0(n=3～50)、1s~22snp~1P_1~0(n=3～50)_和1s~22snd~1D_2(n=3～50)里德堡系列能级和量子亏损.计算结果与已有的实验结果符合得很好.     

具有宽过冷液相区的Fe62 Co8-x(Cr,Mo)xNb4 Zr6 B2非晶态合金的热稳定性与磁性

根据制备块状非晶态合金的三条经验准则,选择了成分为Fe62Co8-xCrxNb4Zr6B20和Fe62Co8-xMoxNb4Zr6B20(x=0,2,4)的合金系.利用单辊急冷法制备出厚为30μm宽为5mm左右的条带,并用差热分析、X射线衍射以及Faraday磁天平、静态磁性测量仪等研究了合金的热稳定性、非晶结构和磁性能.发现含2at%Cr的Fe62Co6Co6Nb4Zr20B20非晶态合金的过冷液相区ΔTx最宽,达到85K,但是合金系的饱和比磁化强度σs随Cr或Mo含量的增加而急剧下降.合金系经973K真空退火900s后,由于晶化相α-Fe等晶相析出,使得各合金的σx和Hc都迅速升高.     

具有宽过冷液相区的Fe62Co8—x（Cr,Mo）xNb4Zr6B20非晶态合金的热稳定性与磁性

根据制备块状非晶态合金的三条经验准则,选择了成分为Fe62Co8-xCrxNb4Zr6B20和Fe62Co8-xMoxNb4Zr6B20(x=0,2,4)的合金系,利用单辊急冷法制备出厚为30μm宽为5mm左右的条带,并用差热分析,X射线衍射以及Faraday磁天平,静态磁性测量仪等研究了合金的热稳定性,非晶结构和磁性能,发现含2at%Cr的Fe62Co6Cr2Nb4Zr6B20非晶态合金的过冷液相区ΔTx最宽,达到85K,但是合金系的饱和磁比强度σs随Cr或Mo含量的增加而急剧下降,合金系经973K真空退火900s后,由于晶化相α-Fe等晶相析出,使得合金的σs和Hc都迅速升高。     

Mg_2B_n(n=4～9)团簇结构与性质的DFT研究

用密度泛函理论(DFT)的B3LYP方法在6-31G*的基组水平上对Mg2Bn(n=4～9)团簇的各种可能的几何构型进行优化,得到了Mg2Bn(n=4～9)团簇的最稳定结构,并对其几何结构、振动光谱、电离能、能隙、电荷布局、成键特性等性质进行了计算.结果表明:Mg2Bn(n=4～9)团簇中大部分B原子为负电性且总是处在团簇的中心,Mg原子总是处在端位上并显正电性;随着n的增大,团簇最稳定结构逐渐由平面结构向立体结构转变;n=4、8时的结构相对较稳定.     

Co对单层MoS_2电子结构与磁性的影响

为了研究Co对单层MoS_2电子结构和磁性的影响,本文基于第一性原理,采用数值基组的方法计算了Co吸附式掺杂、Co替代式掺杂单层MoS_2的能带结构、态密度以及分析了其结构的稳定性.结果发现:Co替换式掺杂体系的形成能较低,实验上容易实现;Co在Mo位吸附的稳定性强于在S位吸附;Mo位吸附体系的总磁矩为0.999μB,其磁矩的主要来源于Co原子的吸附所贡献的0.984μB,Co原子的掺杂体系总磁矩为1.029μB,其磁矩的主要由Co原子替代掉一个Mo原子所贡献的磁矩为0.9444μB,相比于吸附体系,Co原子对磁矩的贡献率有所降低;无论是Co吸附在单层MoS_2表面还是Co直接替代掉Mo原子的掺杂体系,Co原子3d轨道的引入是引起单层MoS_2体系磁性的主要原因.     

第一性原理研究Co2MnSi和Co2MnGe半金属与磁性的稳定性

基于广义梯度近似密度泛函和全势能线性缀加平面波方法,对Co2MnSi和Co2MnGe在晶格常数发生变化的情况下进行电子结构和磁矩的自旋极化计算,得到了它们的自旋态密度分布以及总磁矩和各原子磁矩。计算结果的分析表明：（1）Co2MnSi 和Co2MnGe具有半金属性质;（2）晶格常数的改变分别为-5%~ 4%和-6%~1%时,Co2MnSi 和 Co2MnGe仍保持稳定的半金属质性;（3）Co2MnSi 和Co2MnGe的总磁矩为5.00µB/formula。总磁矩主要来源于Mn和Co的原子磁矩,Si和Ge的原子磁矩对总磁矩的贡献极小而且为负值。（4）Co2MnSi 和 Co2MnGe的晶格常数变化分别为-6% ~ 6%和-7%~ 4%时,虽然各原子磁矩都发生了变化,但是它们总磁矩稳定于5.00µB/formula.     

Fe、Co、Ni混合团簇磁性的密度泛函研究

基于13原子二十面体结构,采用密度泛函方法系统计算研究了Fe、Co及Ni单质及二元混合团簇的磁性.发现有限温度下团簇磁性随结构畸变的敏感性随Fe、Co、Ni顺序逐渐减弱,同时发现二十面体结构Fe_(13)及Co_(13)均具有不同磁矩的近简并低能态.对FeNi及CoNi混合团簇、其磁矩随组分的变化不存在反常现象,但对于FeCo混合团簇、其磁矩随组分的演化行为存在个别反常现象.我们认为:这种反常现象能够对FeCo非晶合金中的实验观测结果提供一种可能的理论解释.     

Electronic and magnetic properties of free and supported transition metal clusters

The spin-polarized relativistic version of the multiple scattering or the Korringa–Kohn–Rostoker method for electronic structure calculations has been used to study the electronic and magnetic properties of free and supported transition metal clusters. Corresponding results are presented for the spin- and spin–orbit-induced orbital magnetic moments in free Fe and FePt clusters. For both systems a pronounced enhancement is found for the spin as well as for the orbital moments compared with the corresponding bulk value which diminishes in an oscillatory fashion with increasing cluster size. Corresponding investigations on small Co clusters deposited on a Pt (111) surface also revealed a strong dependence of the magnetic properties on the cluster size and shape. A comparison of our theoretical results with available experimental data led to rather satisfying agreement.     

Co-B amorphous alloy nanochains with enhanced magnetization and electrochemical activity prepared in a biphasic system

Co-B amorphous alloy in the form of nanochains was prepared by chemical reduction of cobalt ions with borohydride in a dodecanethiol/water biphasic system. Such Co-B nanochains were comprised of uniform Co-B nanoparticles connected in one-dimension through electrostatic force between the induced dipoles. Dodecanethiol molecules played a key role in the formation of Co-B nanochains by covering Co-B nanoparticles via strong chemisorption bond which stabilized Co-B nanoparticles against gathering and also generated induced electric dipoles. The linear array of Co-B amorphous alloy nanoparticles resulted in the superposition of magnetic moments and also facilitated the electron transfer, leading to the enhanced magnetization and electrochemical activity.     

Absence of zero-bias anomaly in spin-polarized vacuum tunneling in Co(0001)

In a joint experimental and theoretical study, we investigate the bias-voltage dependence of the tunnel magnetoresistance (TMR) through a vacuum barrier. The TMR observed by spin-polarized scanning tunneling microscopy between an amorphous magnetic tip and a Co(0001) sample is almost independent of the bias voltage at large tip-sample separations. Whereas qualitative understanding is achieved by means of the electronic surface structure of Co, the experimental findings are compared quantitatively with bias-voltage dependent first-principles calculations for ballistic tunneling. At small tip-sample separations, a pronounced minimum in the experimental TMR was found at +200 mV bias.     

Amorphous Cobalt Boride Alloy Synthesized by Liquid Phase Methods as Electrode Materials for Electrochemical Capacitors

An amorphous cobalt boride alloy with high electronic conductivity is fabricated through the liquid-phase reduction method. Benefiting from large specific surface area and hierarchical pore structure, the as-synthesized Co-B nanoflakes expose substantial electrochemical active sites, promote the transfer of electrons and ions, and accelerate the redox kinetic process. The as-obtained amorphous Co-B alloy sample displays a specific capacitance of 411 F g⁻¹ at 0.5 A g⁻¹, and with the current density increased to 10 A g⁻¹, it maintains 69% of the initial capacitance. The as-assembled asymmetric supercapacitor device reveals electrochemical properties comprising an excellent specific capacitance of 64.3 F g⁻¹ at 0.25 A g⁻¹, superior cyclical stability of 105% after 20,000 cycles at 3 A g⁻¹, and maximum energy density of 22.9 Wh kg⁻¹ at a power density of 200.3 W kg⁻¹. This study demonstrates great potential in developing high-conductivity materials for an asymmetric supercapacitor through utilizing an amorphous cobalt boride alloy as a promising electrode material.     

非晶态稀土合金Tb-Co的电子结构

用X射线光电子能谱研究了非晶态稀土合金Tb_xCo_1-x的电子结构。比较晶态和非晶态:他们的导带、4f带以及芯态谱没有明显差别,说明Tb-Co之间电荷的转移对两种状态没有什么区别,因而两种状态下磁性的差别不能解释为电荷转移量的不同。 关键词：     

Magnetic properties of Co–Si alloy clusters

We have investigated the electronic structure and the magnetic properties of Co–Si alloy clusters using ab initio spin-polarized density functional calculations. The possible CoSi₂, CoSi, and Co₂Si phase clusters with oblique hexagon prism, icosahedron, and cuboctahedron structures are introduced. The CoSi phase cluster with icosahedron structure has the largest binding energy and amount of charge transfer. We found that HOMO-LUMO gap, magnetic moment, and spin polarization for the Co–Si alloy clusters with icosahedron structure increase with Co concentration. The Si atoms in the CoSi phase with icosahedron structure have negative magnetic moment.     

Formation of quaternary all-d-metal Heusler alloy by Co doping fcc type Ni2MnV and mechanical grinding induced B2-fcc transformation

The structure of the all-d-metal alloy Ni$_{50-x}$Co$_{x}$Mn$_{25}$V$_{25}$ ($x = 0$-50) is investigated by using theoretical and experimental methods. The first-principles calculations indicate that the most stable structure of the Ni$_{2}$MnV alloy is face-centered cubic (fcc) type structure with ferrimagnetic state and the equilibrium lattice constant is 3.60 Å, which is in agreement with the experimental result. It is remarkable that replacing partial Ni with Co can turn the alloy from the fcc structure to the B2-type Heusler structure as Co content $x > 37$ by using the melting spinning method, implying that the d-d hybridization between Co/Mn elements and low-valent elements V stabilizes the Heusler structure. The Curie temperature $T_{\rm C}$ of all-d-metal Heuser alloy Ni$_{50-x}$Co$_{x}$Mn$_{25}$V$_{25}$ ($x > 37$) increases almost linearly with the increase of Co due to that the interaction of Co-Mn is stronger than that of Ni-Mn. A magnetic transition from ferromagnetic state to weak magnetic state accompanying with grinding stress induced transformation from B2 to the dual-phase of B2 and fcc has been observed in these all-d-metal Heusler alloys. This phase transformation and magnetic change provide a guide to overcome the brittleness and make the all-d-metal Heusler alloy interesting in stress and magnetic driving structural transition.     

MgmBn(m=1,2;n=1—4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G基组水平上对Mg_mB_n(m=1,2;n=1-4)团簇各种可能的构型进行几何结构优化，预测了各团簇的最稳定结构.并对最稳定结构的振动特性、电离势、成键特性、极化率和超极化率等性质进行了理论研究.结果表明，团簇的最稳定结构大多是平面结构，团簇的稳定结构中通常是几个呈负电性的B原子形成一个负电中心，而其他B原子和Mg原子通常处在端位，且显正电性；团簇中通常是B-B键和B-Mg键共存，极少出现Mg-Mg键， 关键词： mB_n(m=1')" href="#">Mg_mB_n(m=1 n=1-4)团簇 密度泛函理论 结构与性质