LaCoO3中自旋态转变现象的超声研究

测量了LaCoO3单相多晶样品的纵波与横波超声声速和衰减随温度的变化关系, 在材料的自旋态转变温度附近(≈90K),纵波声速出现明显的软化并伴随一个尖锐的衰减峰,但是在横波的测量中却没有出现类似的超声异常,分析认为LaCoO3在90K附近的自旋态转变是由于Co3+离子是从低自旋态(LS,t62ge0g)转变到中等自旋态(IS,t52ge1g ),而不是高等自旋态(HS,t42ge2g).随着温度的升高,在200K附近纵波和横波测量上都观察到一个伴随着微小声速软化的宽大的衰减峰,这可能是随机分布的IS态Co3+离子的Jahn-Teller效应导致的局域晶格扭曲所造成的.     

La0.7Sr0.3-x□xCoO3(0≤x≤0.2)钴氧化物中锶空位诱导的自旋态转变效应

研究了锶空位对La_0.7Sr_0.3-x_xCoO₃ (0≤x≤0.2)多晶钴氧化物结构、磁性和输运性质的影响.结果表明：随着锶空位浓度x的增大,A位阳离子无序度增大,导致铁磁双交换作用减弱及反铁磁超交换作用增强,两者相互竞争,出现团簇自旋玻璃态;空位浓度超过10%后,Co—O键长迅速减小,导致晶体场劈裂能加大,大部分三价钴离子以低自旋态出现,系统基态为类超顺磁态, 关键词： 空位掺杂 钴氧化物 自旋转变     

GaMnN铁磁共振隧穿二极管自旋电流输运以及极化效应的影响

通过理论计算研究GaMnN铁磁共振隧穿二极管自旋电流输运特性.理论结果表明在电流特性曲线上出现两个明显的自旋分裂峰.该电流自旋分裂峰和相应的自旋极化随温度的升高而逐渐减小消失.当进一步考虑到GaN异质结界面极化电荷影响时,自旋向下的电流共振峰得到明显增强,同时电流的自旋极化也得到相应的提高.在一定的极化电荷条件下,可以获得较高的自旋极化电流. 关键词： GaMnN 共振隧穿 自旋电流 极化电荷     

从Sn质子滴线核到Sn中子滴线核的自旋对称性和赝自旋对称性

在球形相对论平均场模型下, 采用NLSH相互作用全面研究了从Sn质子滴线核到Sn中子滴线核的自旋对称性和赝自旋对称性. 发现: 1) 随着核子数的增大, 中子和质子的赝自旋波函数劈裂基本上都是减小的, 并且质子的变化趋势更加明显. 中子高能级的自旋波函数劈裂随着核子数的增大也是减小的. 2) 对于特定的同位素, 当n=1时, 赝自旋波函数劈裂随着l的增大而增大. 当n=2时, 中子的自旋波函数劈裂随着l的增大而增大. 当l=2或l=3时, 中子的自旋波函数劈裂随着n的增大而增大. 3) 中子和质子的赝自旋劈裂之间的差别总是比自旋劈裂的差别更大一些.     

六配位FeN6自旋翻转化合物的自旋输运特性

本文采用第一性原理计算和非平衡格林函数方法,研究了六配位FeN₆的自旋输运特性. 理论计算结果表明在外场(如光辐射)作用下通过改变配体与磁芯间键长来实现磁体的高低自旋之间的转换. 基于计算得到的透射谱和伏安曲线,发现通过高自旋态分子结的电流显著大于低自旋态磁体,且通过高自旋态分子结的输运特性由自旋向下的电子提供主要贡献. 理论预测出来的分子开关和自旋过滤效应表明此类铁基六配体自旋翻转化合物可用于分子自旋电子学器件设计.     

LaCoO3中自旋态转变现象的超声研究

测量了LaCoO₃单相多晶样品的纵波与横波超声声速和衰减随温度的变化关系, 在材料的自 旋态转变温度附近（≈90K），纵波声速出现明显的软化并伴随一个尖锐的衰减峰，但是在 横波的测量中却没有出现类似的超声异常，分析认为LaCoO₃在90K附近的自旋态 转变是由于Co³⁺离子是从低自旋态(LS,t⁶_2ge⁰ _g)转变到中等自旋态(IS,t⁵ _2ge¹_g )，而不是高等自旋态(HS,t⁴_2ge²_g).随着温度的升高，在 200K附近纵波和横波测量上都观察到一个伴随着微小声速软化的宽大的衰减峰，这可能是随 机分布的IS态Co³⁺离子的Jahn-Teller效应导致的局域晶格扭曲所造成的. 关键词： 超声声速与衰减 自旋态转变 Jahn-Teller效应     

Woods-Saxon势下的赝自旋对称性

通过求解具有Woods-Saxon径向标量势与矢量势的Dirac方程, 分别分析了原子核中赝自旋双重态能级劈裂和波函数下分量劈裂随着Woods-Saxon势参数的变化关系, 其中Wood-Saxon势中的参数a以及R对于赝自旋能级劈裂和波函数劈裂的影响最大, 而势阱深度V₀只产生微小的影响. 随着平均场的变化, 赝自旋双重态会出现能级反转现象. 具有较大n或l的赝自旋双重态能级劈裂对于参数的变化更敏感. 赝自旋波函数下分量劈裂随着参数a和R的增大向核表面扩散, 并且在核表面附近达到最大. 赝自旋波函数劈裂随着参数a的增大而增大, 但是随着参数R或V₀的增大它却在减小的. 由于在特定的同位素链中, 参数R和V₀都与核子数有关系, 而参数a又是描述核的表面性质的, 所以以这些参数为变量对于赝自旋劈裂的研究是有意义的, 研究的结果至少在定性上可以应用到大部分原子核中.     

基因开关体系多稳性质的时间延迟效应

利用延迟随机模拟方法,研究了时间延迟τ对一种基因开关体系中多稳性质的影响．这种基因开关体系在不存在时间延迟时,依据转录因子结合速率?的不同,可以表现出蛋白质高表达态、低表达态 以及高低表达共存态等多稳特性．研究发现,时间延迟可以抑制共存态中的一种表达态从而实现到另一种表达态的转变．通过计算α-τ参数空间的相图,进一步揭示了随着延迟时间的增加,共存态的参数区间会显著缩小;当延迟时间大于某个三相点时,共存态消失;高和低表达态可不通过共存态实现直接转变．     

La0.7Sr0.3-x□xCoO3(0≤x≤0.2)钴氧化物中锶空位诱导的自旋态转变效应

研究了锶空位对La0.7Sr0.3-x□xCoO3(0≤x≤0.2多晶钴氧化物结构、磁性和输运性质的影响.结果表明:随着锶空位浓度x的增大,A位阳离子无序度增大,导致铁磁双交换作用减弱及反铁磁超交换作用增强,两者相互竞争,出现团簇自旋玻璃态;空位浓度超过10%后,Co-O键长迅速减小,导致晶体场劈裂能加大,大部分三价钴离子以低自旋态出现,系统基态为类超顺磁态,同时样品发生金属-绝缘体相变.     

铁磁材料GdN的电子结构和磁学性质的理论研究

作为寻找新型自旋电子学功能材料的尝试，文章详细研究了稀土化合物GdN的电子结构和磁学性质，通过第一性原理的理论计算，作者发现该材料的导电性质随体积增加有很大变化：从半金属态到准金属态，最后成为半导体．同时，施加压力能改变其载流子浓度和位于多数自旋态的电子和空穴的迁移率．对其磁交换参数随品格常数变化的进一步研究和蒙特卡罗模拟表明，这个铁磁体系的居里温度可以通过加压或掺杂得到进一步提高，从而成为很有实用价值的自旋电子材料．     

Hydrostatic pressure driven spin,volume and band gap collapses in SmFeO3: a GGA + U study

The crystal structure, magnetic and electronic properties of SmFeO₃ under hydrostatic pressure have been studied by first-principles calculations within the generalized gradient approximation plus Hubbard U (GGA + U). The iso-structural phase transition with spin, volume and band gap collapses can be induced by a large enough hydrostatic pressure. The high-spin (HS) state of Fe³⁺, with the magnetic moment of ~4 μ_B, is retained at low pressure. The spin crossover occurs at a transition pressure (~68 GPa) with the magnetic moment of Fe³⁺ decreasing to ~1 μ_B in low-spin (LS) state. Meanwhile, the reductions of cell volume (by ~?5.43%) and band gap (from >2 eV to ~1.6 eV) of SmFeO₃ are obtained when the HS–LS transition happens. Finally, the critical pressure of HS–LS transition, magnetic and electronic properties are found to be Hubbard U dependent.     

Thermal trapped iron(II) high spin state investigated by X-ray diffraction

The possibilities to trap by flash cooling the high spin (HS) state of iron(II) in the [Fe(PM-BiA)₂(NCS)₂] complex have been investigated by X-ray diffraction. This study reveals that trapping the HS state is possible under some conditions depending on the final temperature. If the latter is lower than the T(LIESST) temperature, the HS→LS (low spin) relaxation is slow enough to determine the trapped HS crystal structure by X-ray diffraction. The crystal structure of this complex in the 30 K trapped HS state shows differences from either the room temperature (HS) or the 30 K (LS) crystal structures, as for example differences in the strength of the S?H-C hydrogen bond like intermolecular interaction or the π-π interactions, known to play a crucial role in this compound for the propagation of the change in spin at the spin crossover (SCO), i.e. the cooperativity. The differences in intermolecular interactions are directly linked to the differences between the crystallographic unit cell modifications induced by pure thermal effects and those induced by the SCO.     

New Hofmann-like spin crossover compound with 3,5-lutidine

A new type III of 3,5-lutidine spin crossover coordination compound with formula Fe(3,5-lutidine)₂Ni(CN)₄·2[(H₂O)(3,5-lutidine)] 2c has been obtained. The ratio of the high spin state (HS) iron (II) changing to the low spin state (LS) iron (II) in 2c is higher than that of type I and type II 3,5-lutidine coordination polymer 2a and 2b previously reported. ⁵⁷Fe Mössbauer spectra of 2c show two different doublets which correspond to HS1 (inner doublet lines) and HS2 (outer doublet lines). The intensity of the HS1 doublet decreases on cooling to 80 K while the intensity of another component, the LS singlet, increases. The 90 % of the HS1 doublet change to the LS singlet is probably due to suitable environments of octahedral iron (II) ions coordinated by four nitrogen atoms of cyano groups and two nitrogen atoms of 3,5-lutidine ligands. We also prepared the Hofmann-like 3,5-dichloropyridine coordination compound Fe(3,5-dichloropyridine)₂Ni(CN)₄ ·2[(3,5-dichloropyridine)(H₂O)] 2d to compare it with 2c. ⁵⁷Fe Mössbauer spectra of 2d show that 2d is not a spin crossover coordination compound.     

Terahertz Cyclotron Photoconductivity in a Highly Unbalanced Two-Dimensional Electron–Hole System

The magnetic properties of the α-Fe₂O₃ hematite at a high hydrostatic pressure have been studied by synchrotron Mössbauer spectroscopy (nuclear forward scattering (NFS)) on iron nuclei. Time-domain NFS spectra of hematite have been measured in a diamond anvil cell in the pressure range of 0–72 GPa and the temperature range of 36–300 K in order to study the magnetic properties at a phase transition near a critical pressure of ~50 GPa. In addition, Raman spectra at room temperature have been studied in the pressure range of 0–77 GPa. Neon has been used as a pressure-transmitting medium. The appearance of an intermediate electronic state has been revealed at a pressure of ~48 GPa. This state is probably related to the spin crossover in Fe³⁺ ions at their transition from the high-spin state (HS, S = 5/2) to a low-spin one (LS, S = 1/2). It has been found that the transient pressure range of the HS–LS crossover is extended from 48 to 55 GPa and is almost independent of the temperature. This surprising result differs fundamentally from other cases of the spin crossover in Fe³⁺ ions observed in other crystals based on iron oxides. The transition region of spin crossover appears because of thermal fluctuations between HS and LS states in the critical pressure range and is significantly narrowed at cooling because of the suppression of thermal excitations. The magnetic P–T phase diagram of α-Fe₂O₃ at high pressures and low temperatures in the spin crossover region has been constructed according to the results of measurements.     

Spin-State Transitions in an Iron Spin-Crossover Complex Observed with X-ray Emission and X-ray Absorption

The thermal- and photon-induced phase transitions of [Fe(2-pic) 3 ]Cl 2 EtOH from a high-spin (HS) state ( S = 2) to a low-spin (LS) state ( S = 0) were observed by X-ray Emission Spectroscopy (XES) and X-ray Absorption Spectroscopy (XAS). The spin state was observed with Fe 3p-1s XES from the HS and photon-induced (PI) phase took S = 2 and LS state took S = 0. Each spectrum of the decay process from the PI phase to the LS state could be described with the superposition of those of the HS and LS states. In XAS, a different spectrum was also observed in the HS and LS states, and likewise by XES; the difference in the pre-edge structure between the HS and LS states was explained based on the difference of Fe unoccupied 3d partial density of state calculated by the DV-X f method.     

菱铁矿FeCO3高压相变与性质的第一性原理研究

采用平面波赝势方法对菱铁矿FeCO₃高压下的晶体结构, 电子构型和电子结构进行了第一性原理计算研究. 研究过程中考虑了菱铁矿FeCO₃真实的反铁磁(AFM) 自旋有序态, 模拟静水压环境, 从零压逐步加压到500 GPa. 在40---50 GPa压力范围内, FeCO₃发生了从高自旋(HS) AFM态到低自旋(LS) 非磁性(NM) 态的磁性相变, 伴随着晶胞体积坍塌10.5%. FeCO₃在相变前后均是绝缘体, 但是相变后的LS-NM态的Fe²⁺ 离子的3d电子局域化程度更强, 能隙随着压力的进一步增大而逐步增大, 离化程度更高, 直到500 GPa没有发生金属绝缘体相变.     

Spin transition in magnesiowüstite in earth's lower mantle

Iron in the major lower mantle (LM) minerals undergoes a high spin (HS) to low spin (LS) transition at relevant pressures (23-135 GPa). Previous failures of standard first principles approaches to describe this phenomenon have hindered its investigation and the clarification of important consequences. Using a rotationally invariant formulation of LDA + U we report a successful study of this transition in low solute concentration magnesiowüstite, (Mg(1-x)Fe(x)(O), (x < 0.2) the second most abundant LM phase. We show that the HS-LS transition goes through an insulating (semiconducting) intermediate mixed spins (MS) state without discontinuous changes in properties, as seen experimentally. We show that the HS state crosses over smoothly to the LS state passing through an insulating MS state where properties change continuously, as seen experimentally.     

Mössbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy)2[Pd(CN)4]

⁵⁷Fe Mössbauer spectroscopic results on the alternatively prepared spin crossover coordination polymer Fe(3-Clpy)₂Pd(CN)₄ sample I agree with those of SQUID data. Mössbauer specrum at RT shows two diffrent doublets which correspond to the HS1(inner doublet) and HS2(outer doublet). The intensity of the HS1 doublet decreases on cooling to 78 K at the expense of a new one featuring the LS singlet. Almost 100 % of HS1 change to LS singlet due to iron(II) ions coordinated by four N atoms of cyano groups and two N atoms of 3-Clpy ligand in the sample I. The SQUID data of the sample I prepared by a new direct contact method are different from those of the already reported Fe(3-Clpy)₂Pd(CN)₄ sample. The differences of the SQUID data are associated with particle size effects in molecule spin crossover samples.     

Determination of Spin State in Dinuclear Iron(II) Coordination Compounds Using Applied Field Mössbauer Spectroscopy

So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high spin (HS) and low spin (LS) species have been deduced from magnetic susceptibility and zero field Mössbauer spectroscopy data irrespective of whether they belong to LS-LS, LS-HS and HS-HS pairs. However, the distinction of pairs becomes possible if Mössbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.

     

Quench dynamics in spin crossover induced by high pressure

In this paper we have analytically and numerically studied the dynamics of spin crossover induced by time-dependent pressure. We show that quasi static pressure, with a slow dependence on time, yields a spin crossover leading to transition from the high spin (HS) quantum system state to the low spin (LS) state. However, quench dynamics under shockwave load are more complicated. The final state of the system depends on the amplitude and pulse velocity, resulting in the mixture of the HS and LS states.