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.     

钠玻璃与钛玻璃在静水压下的弹性性能

用超声脉冲重叠法测量了钠玻璃(float glass)和钛玻璃(SiO₂+8.4wt%TiO₂)从大气压到2GPa静水压条件下的纵波声速和横波声速.发现两种玻璃有不同的变化规律.钛玻璃的纵波声速和横波声速,与钠玻璃的横波声速都随压力的增加而减小;而钠玻璃的纵波声速随压力的增加先增大,后减小.这一现象不同于别的氧化硅玻璃.对实验结果进行了讨论,并计算了弹性模量在压力下的变化和Murnaghan状态方程参数. 关键词： 高压 超声 玻璃     

Ultrasonic Study on Jahn-Teller Distortions in La1=3Sr2=3CoO3

系统研究了La1=3Sr2=3CoO3单相多晶样品在低温下的电磁输运性质和超声特性．电阻率测量表明,La1=3Sr2=3CoO3在整个温区内都表现出金属特性,并且在235 K处电阻率-温度曲线的斜率发生了变化,同时伴随着铁磁相变．超声声速在铁磁相变温度以下出现软化,并在120 K附近达到最小,之后,随着温度的进一步降低,声速开始硬化,同时出现了一个宽大的超声衰减峰．分析认为,该超声异常可能起源于中等自旋态Co3+的Jahn-Teller效应．     

非晶态快离子导体(AgI)x(Ag4P2O7)1-x的声学性质

用液氮骤冷方法制备了(AgI)_x(Ag₄P₂O₇)_1-x系列非晶态快离子导体。对AgI摩尔浓度x=0.50,0.60,0.67,0.75,0.80的样品,在77—300K温度范围及2,5,10,15MHz的频率上测量了纵波和横波的超声衰减和声速。发现在200—240K附近存在一个异常强的弛豫型超声吸收峰,随AgI含量的增加,该峰的位置向低温方向移动,且峰的高度增大。在实验的温度范围内,观察到纵波和 关键词：     

准一维反铁磁体CsMnCl3·2D2O中激子的能量转移

在2—300K温度范围,研究了纯的及掺Mg²⁺,Ni²⁺和Co²⁺的准一维反铁磁体CsMnCl₃·2D₂O(CMC)中Mn²⁺离子的⁴T₁激子的能量转移动力学过程,发现在2—10K范围,激子的荧光强度和寿命随温度很快下降,较高浓度的杂质离子将进一步加快荧光的减弱和寿命的缩短。这种现象被归结为与磁相互作用和自旋有序相关联的多声子无辐射跃迁及施主—受主之间的能量转移。在更高的温度,能量转移速率增高,但由于仍然存在的自旋短程有序和Jahn-Teller效应,施主之间的能量迁移受到一定限制,出现非指数衰减过程。各种不同的杂质离子在某种程度上显示出不同的陷落作用和弛豫特性。 关键词：     

掺入Mg2+对CsNiCl3晶体的基态能级、零场分裂参量及Jahn-Teller效应的影响

应用不可约张量理论构造了三角对称晶场中3d²/3d^８态离子的45阶可完全对角化的微扰哈密顿矩阵，在考虑了以前工作中被忽略的自旋-自旋耦合作用的基础上计算了CsNiCl₃晶体和CsNiCl₃:Mg²⁺晶体的基态能级、晶体结构、零场分裂参量和Jahn-Teller效应，研究了掺入Mg²⁺对CsNiCl₃晶体的光谱、零场分裂参量及Jahn-Teller效应的影响和自旋单重态对基态能级的贡献，发现掺杂使得晶体结构产生畸变，从而改变晶体光谱的精细结构和零场分裂参量，不改变Jahn-Teller效应的分裂规律但改变分裂的大小. 关键词： 基态能级 掺杂 零场分裂 自旋-自旋耦合     

S2分子B″3Πu态的势能函数和光谱常数的理论研究

推导了S₂分子B″³Π_u态的合理离解极限.用Gaussian 94 QCISD(T)方法和6-311++G^**基组计算了S₂分子B″³Π_u以及X³Σ^-_g态的势能曲线.给出了S₂分子B″³Π_u态的Murrell-Sorbie势能函数和光谱常数.B″³Π_u与B³Σ^-_u态在排斥支重叠范围大；同时，B″³Π_u与X³Σ^-_g态有相同离解极限，因而，在吸引支有重叠.讨论了B″³Π_u与B³Σ^-_u和X³Σ^-_g态相互作用的特征. 关键词：     

Co掺杂对铁磁金属La0.8Sr0.2MnO3磁电阻影响机理

通过对La_0.8Sr_0.2Mn_1-yCo_yO₃(y≤02)饱和磁矩和输运的测量,研究了Co对La_0.8Sr_0.2MnO₃的磁电阻影响机制.结果表明,在La_0.8Sr_0.2Mn_1-yCo_yO₃（y≤02）中Co³⁺离子是低自旋态.由于Mn³⁺—O—Co³⁺—O—Mn³⁺类型的磁交换与Mn³⁺-Mn⁴⁺离子间双交换作用相比较弱,Curie温度T_C附近的磁电阻随着Co掺杂量的增加而降低.与此相反,由于Co²⁺离子与e_g巡游电子的反铁磁交换耦合作用,低温区间的磁电阻随着Co掺杂量的增加而升高. 关键词： 低自旋 磁电阻 磁交换作用     

La0.67Sr0.33Mn0.87Fe0.13O3的超声性质研究

测量了Ｌａ０．６７Ｓｒ０．３３Ｍｎ０．８７Ｆｅ０．１３Ｏ３多晶单相样品的电阻,超声声速和衰减随温度的变化。发现超声衰减在１５０Ｋ附近出现一个峰值,同时电阻迅速增加,表明样品中存在极化子－声子耦合作用。在８５Ｋ附近样品由半导体转变为金属,但当Ｔ〈６０Ｋ时样品又变成半导体行为,同时超声声速出现一个很小的软化,这表明样品中可能存在自旋玻璃态。     

多相氧载体CoO-MgO和氧分子作用的ESR研究

用ESK研究多相氧载体CoO-MgO表面上氧的吸附作用,发现在77-150K温度范围内表面Co²⁺离子和O₂的结合是可逆的,吸附产生Co³⁺-O₂^-自由基加合物有超精细结构的ESR谱;当温度增加,吸附态O₂^-自由基发生转移并稳定在Mg²⁺离子上形成Mg²⁺-O₂^-自由基,文中着重讨论Co³⁺-O₂^-自由基的电子结构和成键本质,认为自由基是通过自旋成对的方式形成的,由于σ-л键作用引起的自旋极化以及由于电子离域作用而引起的偶极作用与ESR制的超精细结构线产生有关。     

Structural anomalies associated with the electronic and spin transitions in LnCoO<Subscript>3</Subscript>

A powder X-ray diffraction study, combined with magnetic susceptibility and electric transport measurements, was performed on a series of LnCoO₃ perovskites (Ln = Y, Dy, Gd, Sm, Nd, Pr and La) over a temperature range 100–1000 K. A non-standard temperature dependence of the observed thermal expansion was modelled as a sum of three contributions: (1) weighted sum of lattice expansions of the cobaltite in the diamagnetic low spin state and in the intermediate (IS) or high (HS) spin state. (2) An anomalous expansion due to the increasing population of excited (IS or HS) states of Co³⁺ ions over the course of the diamagnetic-paramagnetic transition. (3) An anomalous expansion due to excitations of Co³⁺ ions to another paramagnetic state accompanied by an insulator-metal transition. The anomalous expansion is governed by parameters that are found to vary linearly with the Ln ionic radius. In the case of the first magnetic transition it is the energy splitting E between the ground low spin state and the excited state, presumably the intermediate spin state. The energy splitting E, determined by a fit to magnetic susceptibility, decreases with temperature. The values of E determined for LaCoO₃ and YCoO₃ at T=0 K are 164 K and 2875 K respectively, which fall to zero at T=230 K for LaCoO₃ and 860 K for YCoO₃. The second anomalous expansion connected with a simultaneous magnetic and insulator-metal transition is characterized by its center at T=535 K for LaCoO₃ and 800 K for YCoO₃. The change of the unit cell volume during each transition is independent of the Ln cation and is about 1% in both cases.     

Sur l'evolution des proprietes physiques de la perovskite GdCoO3 entre 77 et 1200 K

GdCoO₃, which has the GdFeO₃ structure, has been studied between 77 and 1200 K by D.T.A., X-ray diffraction, magnetic susceptibility, electric conductivity and thermoelectric power. All properties observed, although different from those of LaCoO₃, fit with the corresponding Goodenough localized electron model. With rising temperature cobalt ions pass progressively from a low-spin Co^III(t⁶_2ge_g⁰) state to a Co³⁺(t⁴_2ge_g²) high-spin state.     

Covalence-induced stabilization of an intermediate-spin state and the magnetic susceptibility of LaCoO<Subscript>3</Subscript>

The energies of terms with spins S = 0, 1, 2 have been found using exact diagnoalization of the multielectron Hamiltonian of a multiband pd model for the CoO₆ cluster. Co (e _g orbital)-O hops, which form the covalent σ bond, are shown to decrease the energy of the state (IS) with an intermediate spin (S = 1) as compared to the energy of the state (LS) with a low spin (S = 0). An analogue of the Tanabe-Sugano diagram that takes into account the covalence of the CoO₆ cluster is constructed. The state with S = 1 is shown to be a ground state at certain model parameters. An increase in temperature is established to decrease the crystal field and, thus, favors the transition of the ground state from LS to IS at T = 100 K and the transition of the IS ground state to a state (HS) with a high spin (S = 2) at T = 550 K. The magnetic susceptibility of LaCoO₃ is calculated with allowance for the LS, IS, and HS states and for the fact that the HS state exhibits threefold orbital degeneracy of the t _2g shell, which results in an effective orbital moment L = 1 and the importance of spin-orbit interaction. The behavior of this magnetic susceptibility agrees well with the experimental x(T) dependence of LaCoO₃.     

Sign change of the thermoelectric power in LaCoO$_\mathsf{3}$

The substitution of 1%-Ce^{4 +} for La^{3 +} in LaCoO₃ is found to change the sign of the Seebeck coefficient at room temperature. This demonstrates that not only holes but also electrons can be created in LaCoO₃. The result is compatible with the Heikes formula for doping levels close to the pure trivalent Co^{3 +} state. Nonetheless, the physical properties such as magnetic susceptibility, magnetization, thermal conductivity and resistivity are found to be asymmetric for hole and electron-doped LaCoO₃. Such a different behaviour is ascribed to the very different spin-states of Co^{4 +} (low-spin, t _2g ⁵ e _g ⁰) and Co^{2 +} (high-spin, t _2g ⁵ e _g ²).Received: 26 April 2004, Published online: 29 June 2004PACS: 72.15.Jf Thermoelectric and thermomagnetic effects - 75.30.Et Exchange and superexchange interactions - 71.38.-k Polarons and electron-phonon interactions     

Lattice structure and magnetization of LaCoO<Subscript>3</Subscript> thin films

We investigate the structure and magnetic properties of thin films of the LaCoO₃ compound. Thin films are deposited by pulsed laser deposition on various substrates in order to tune the strain from compressive to tensile. Single-phase (001) oriented LaCoO₃ layers were grown on all substrates despite large misfits. The tetragonal distortion of the films covers a wide range from -2% to 2.8%. Our LaCoO₃ films are ferromagnetic with Curie temperature around 85 K, contrary to the bulk. The total magnetic moment is below 1μ _B /Co³⁺, a value relatively small for an exited spin-state of the Co³⁺ ions, but comparable to values reported in literature. A correlation of strain states and magnetic moment of Co³⁺ ions in LaCoO₃ thin films is observed.     

Temperature dependence of the spin state of a Co3+ Ion in RCoO3 (R = La,Gd) cobaltites

Changes in the spin state of Co³⁺ ions in LaCoO₃ and GdCoO₃ compounds are studied through the use of the temperature dependence of the magnetic susceptibility and the modified crystal field theory. It is shown that the spin subsystem of Co³⁺ ions in LaCoO₃ and GdCoO₃ undergoes the spin-crossover type transition between the high-spin (S = 2) and low-spin (S = 0) states without any contribution of the intermediate-spin state (S = 1).     

About the nature of Ni3+ magnetic centres in the LaSrAl1−xNixO4 ceramics

LaSrAl_1?x Ni _x 0₄ (x≤0.11) ceramics werer studied by EPR. It was established that Ni³⁺ ions in this compound may be in two states: a low spin one with t _2g ⁶ e _g ¹ electron configuration and high spin state with t _2g ⁵ e _g ² electron configuration. It was shown that the random distribution of La³⁺ and Sr²⁺ ions in the heavy metal sublattice leads to two kinds for each type of these centres with different degree of tetragonal distortions. The total concentration of NiO₆ isolated centres in these ceramics does not exceed 5–10 % of a total number of nickel ions at a givenx. A model, explaining these peculiarities observed in an experiment by the enhanced tendency of Ni³⁺ ions to clusterization, was proposed. It appears that even at small concentrations Ni³⁺ ions form clusters and conglomerates, whose structural characteristics of the oxygen octahedra are comparable with those in LaSrNiO₄.     

<Superscript>55</Superscript>Mn spin relaxation with the participation of mobile carriers in doped perovskites

Analytical expressions are derived for the rates of longitudinal and transverse nuclear spin relaxation under conditions of fast modulation of the magnitude and direction of a hyperfine field induced by unpaired electrons of an ion. The results obtained are used to explain the data available in the literature on the ⁵⁵Mn spin relaxation in the ferromagnetic metallic phase of doped perovskites, in which the modulation of the hyperfine field is caused by the hopping of e _g electrons between Mn³⁺ and Mn⁴⁺ ions. It is demonstrated that, within this model, the rates of longitudinal and transverse relaxation are characterized by the same temperature dependence and their ratio is independent of temperature, which is in agreement with the experimental data.     

Interplay of structural, magnetic and transport properties in thelayered Co-based perovskite LnBaCo 2 O 5 (Ln = Tb, Dy, Ho)

The oxygen deficient cobaltites LnBaCo₂O₅ (Ln = Tb, Dy, Ho) exhibit two successive crystallographic transitions at T _N ∼340 K and at T _CO ∼210 K. Whereas the first transition (P4/mmm to Pmmm) is related to the long-range antiferromagnetic ordering of the Co ions (spin ordering), the second transition (Pmmm to Pmmb) corresponds to the long-range ordering of the Co²⁺ and Co³⁺ species (charge ordering) occurring in 1:1 ratio in the structure. The charge ordered (CO) state was directly evidenced by the observation of additional superstructure peaks using neutron and electron diffraction techniques. The CO state was also confirmed indirectly from refinement of high resolution neutron diffraction data as well as from resistivity and DSC measurements. From the refined saturated magnetic moment values only, ∼3.7 and ∼2.7 , the electronic configuration of the Co ions in LnBaCo₂O₅ remains conjectural. Two pictures, with Co³⁺ ions either in intermediate spin state ( t ⁵ _2g e ¹ _g ) or in high spin state ( t ⁴ _2g e ² _g ), describe equally well our experimental data. In both cases, the observed magnetic structure can be explained using the qualitative Goodenough-Kanamori rules for superexchange. Finally, in contrast to the parent Ln = Y compound [Vogt et al. , Phys. Rev. Lett. 84, 2969 (2000)], we do not report any spin transition in LnBaCo₂O₅ (Ln = Tb, Dy, Ho). Received 13 December 2000     

Co3+离子自旋态对六方相LaCoO3的低指数晶面稳定性影响的密度泛函理论研究

By the first-principles calculations,most studies indicated that the (11102)-CoO₂ termination of LaCoO₃ cannot be stabilized,which disagrees with the experimental observation.Besides the crystal structure,we found that the spin states of Co³⁺ ions could affect surface stability,which previously were not well considered.By examining the different states of Co³⁺ ions in hexagonal-phase LaCoO₃,including low spin,intermediate spin,and high spin states,the surface grand potentials of these facets are calculated and compared.The results show that the spin states of Co³⁺ ions have an important influence on stability of the LaCoO₃ facets.Different from the previous results,the stability diagrams demonstrate that the (11102)-CoO₂ termination can stably exist under O-rich condition,which can get an agreement with the experimental ones.Furthermore,the surface oxygen vacancy formation energies (E_Ov) of stable facets are computed in different spin states.The E_Ov of these possible exposed terminations strongly depend on the spin state of Co³⁺ ions:in particular,the E_Ov of the HS states is lower than that of other spin states.This indicates that one can tune the properties of LaCoO₃ by directly tuning the spin states of Co³⁺ ions.