Cr~(4 )∶YAG能级结构的全量子力学计算

采用基于分子轨道理论CIS(ConfigurationInteractionofSinglySubstitution)的全量子力学方法计算了掺杂Ca和Cr离子的YAG晶体中 [CrO4 ]4 -团簇离子的能级结构。结果给出了Cr4 团簇 2 0个谱项能级随Cr -O键距的变化 ,对比表明在间距为 173pm时 ,能级结构在可见光及近红外范围的主要光谱特征与实验结果符合得较好     

Cr^4＋：YAG能级结构的全量子力学计算

采用基于分子轨道理论CIS(Configuration Interaction of Singly Substitution)的全量子力学方法计算了掺杂Ca和Cr离子的YAG晶体中[CrO4]^4-团簇离子的能级结构。结果给出了Cr^4 团簇20个谱项能级随Cr-O键距的变化，对比表明在间距为173pm时，能级结构在可见光及近红外范围的主要光谱特征与实验结果符合得较好。     

Cr4+∶YAG固体激光器效率的理论分析

对Cr4 ∶YAG固体激光器的吸收效率、量子效率、储存效率和提取效率等本征效率进行了分析.Cr4 ∶YAG晶体的吸收截面、发射截面、上能级寿命和激活离子浓度等对激光器的本征效率有很大的影响.提高Cr4 ∶YAG晶体的光学品质和激活离子的掺杂浓度,优化泵浦源的运转波长和激光腔的设计都能显著改善Cr4 ∶YAG固体激光器的本征效率.     

Cr4+∶YAG固体激光器效率的理论分析

对Cr4+∶YAG固体激光器的吸收效率、量子效率、储存效率和提取效率等本征效率进行了分析.Cr4+∶YAG晶体的吸收截面、发射截面、上能级寿命和激活离子浓度等对激光器的本征效率有很大的影响.提高Cr4+∶YAG晶体的光学品质和激活离子的掺杂浓度,优化泵浦源的运转波长和激光腔的设计都能显著改善Cr4+∶YAG固体激光器的本征效率.     

Aln(n=2～7)团簇的结构和能级分布

采用密度泛函B3LYP的方法研究了小原子团簇Al2～7的几何结构和能级分布,分析了随团簇原子数的增加,团簇的几何结构和费米能级的变化情况.研究结果表明:Al2～7的团簇的几何结构在5个原子以前为平面结构,而从六个原子开始为空间立体的稳定结构.电子壳层结构表明,在铝团簇中没有出现非常明显的象碱金属那样的稳定幻数结构.在Al2～Al7团簇中,能级结构呈现明显的分立特征,费米能级随着原子个数的增加而减小,到Al7时又有所增加,且团簇的能量间隙最小.     

Ga2Asn离子团簇结构及其光电子能谱研究

利用密度泛函理论中B3LYP方法,在6-311G(d)基组上对Ga2Asn(n=1-5)阴阳离子团簇的几何结构和光电子能谱进行了系统研究.结果得到了各团簇的最稳定结构,在(Ga:Asn(n=1-5)阴阳离子团簇中,稳定性随着总原子数的增大而呈奇偶变化规律,对于(GaAsn-团簇,总原子数为奇数的团簇比原子数为偶数的团簇稳定;对于GazAsn团簇,总原子数为偶数的团簇比原子数为奇数的团簇稳定.团簇的最高占据轨道(HOMO)和最低空轨道(LUMO)能级之间的能隙差随As原子数的增大而呈现奇偶交替变化规律,当As原子数为偶数时,中性团簇及其阴阳离子团簇的基本相同,当As原子数为奇数时,它们差异较大.     

LD泵浦Cr4+∶YAG被动调Q锁模Nd∶Gd0.42Y0.58VO4激光器

理论和实验研究了LD泵浦Nd∶Gd0.42Y0.58VO4/Cr4+∶YAG被动调Q锁模激光器.在分析Cr4+∶YAG晶体能级结构和调Q锁模物理过程的基础上,通过数值模拟给出了Cr4+∶YAG调Q锁模的参量要求,然后进行了实验验证.实验中Cr4+∶YAG的初始透过率T0分别为86.3%、95%,输出镜的透过率T分别为10%、20%,在其他条件不变的情况下构成四种不同的组合,均实现了激光器的调Q锁模运转.实验结果表明,降低Cr4+∶YAG的初始透过率T0或提高输出镜透过率T有利于获得较好的锁模效果,与理论分析一致.     

砷化镓离子团簇的稳定性研究

采用全势能线性糕模轨道分子动力学方法，详细研究了砷化镓离子团簇Ga_nAs_n(n=4，5，6)的几何结构和稳定性.分别找到了这些离子团簇的最低能量结构，通过计算发现这些结构明显不同于中性团簇的基态结构.还发现离子团簇的其他稳定结构与对应的中性结构相比也有较大的结构畸变.在这些砷化镓离子团簇中，相对于砷原子而言，镓原子更容易处在帽原子的位置上. 关键词： 离子团簇 基态结构 稳定性     

Agn(n=2～10)团簇的几何结构和电子特性

应用密度泛函理论中B3LYP/LANL2DZ 方法优化计算并分析了Agn(n=2～10)团簇的基态几何结构及电子性质.同时计算和讨论了银团簇的原子化能、能级分布、能级间隙、电子亲和能和电离势,所得理论计算值与实验值符合较好.研究结果表明:银小团簇的结构不同于块体,且随团簇尺寸大小而相应变化,原子化能和电子亲和势随原子尺寸的增加而增加,团簇的费米能级、电子亲和势和电离势随团簇大小变化具有明显的奇偶振荡特性,并对此作了分析.团簇的电子性质和几何结构之间的密切关系及其随团簇尺寸大小变化的规律,可以从理论上确定团簇的最稳定结构,并可对实验观测结果做出解释.     

Sin-1N和Sin-2N2(n=3～8)离子团簇结构及其光电子能谱的研究

利用密度泛函理论中的B3LYP方法,在6-311G(d)基组上对Sin-1N和Sin-2N2(n=3~8)阴阳离子团簇的几何结构和光电子能谱进行了系统研究。结果得到了各团簇的最稳定结构,Sin-2N2离子团簇对称性比Sin-1N离子团簇对称性好;Sin-1N(n=3~8)离子团簇的几何结构在总原子数n≤4时为平面结构,n>4时为立体结构;Sin-2N2(n=3~8)离子团簇的几何结构在总原子数n≤6时为平面结构,n>6时为立体结构;对于Sin-1N 团簇,总原子数是偶数的团簇比总原子数为奇数的团簇稳定;对于Sin-1N-及Sin-2N2阴阳离子团簇,总原子数是奇数的团簇比总原子数为偶数的团簇稳定。     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：     

Li3VO4-Li4SiO4-Li4GeO4赝三元系相图的研究

本文用差热分析法和高温、室温X射线衍射法对Li₃VO₄,Li₄SiO₄的相变过程,Li₃VO₄-Li₄SiO₄,Li₃O₄-Li-4GeO₄赝二元系相图以及Li₃VO₄-Li₄SiO₄-Li₄GeO₄赝三元系相图室温截面进行了研究。发现在Li₃VO₄-Li₄SiO₄,Li₃VO₄-Li₄GeO₄赝二元系中,由于Li₄SiO₄或Li₄GeO₄的加入而使Li₃VO₄的高温γ_II相稳定存在于室温,从而得到一种新的具有高电导率的锂离子导体。作者认为探寻使高温态稳定存在于室温的方法是探索新的离子导体研究中有效途径之一。 关键词：     

NH4H2PO4和ND4D2PO4晶体微结构的拉曼光谱研究

本文利用偏振拉曼光谱和第一性原理, 对磷酸二氢铵(NH₄H₂PO₄, ADP)和不同氘含量磷酸二氢铵DADP晶体的晶格振动模式进行了研究. 实验测得了不同几何配置、200–4000 cm^-1范围的偏振拉曼光谱, 分析在不同氘含量条件下921 cm^-1和3000 cm^-1附近拉曼峰的变化. 在ADP晶体中, 基于基本结构单元NH₄⁺ 和H₂PO₄^-基团的振动模, 用第一性原理进行了数值模拟, 进一步明确拉曼峰与晶体中原子振动的对应关系; 通过洛伦兹拟合不同氘含量DADP晶体的拉曼光谱中2000–2600 cm^-1处各峰的变化讨论了DADP 晶体的氘化过程, 结果表明氘化顺序是先NH₄⁺ 基团后H₂PO₄^-基团, 研究结果为今后此类材料的生长和性能优化奠定了基础.     

Ion diffusion in the high-temperature phases Li2SO4, LiNaSO4, LiAgSO4 and Li4Zn(SO4)3

Diffusion in the four high-temperature sulphate phases Li₂SO₄, LiNaSO₄, LiAgSO₄ and Li₄Zn(SO₄)₃ was studied extensively some 20–30 years ago. We have now carried out a re-evaluation where we include information obtained from a number of studies of other properties. The data are adjusted slightly due to the use of another type of regression analysis. It is characteristic of the four phases that they are both plastic crystals and solid electrolytes (superionic conductors). The cause of the high conductivity is that the mobility of the cations is strongly enhanced by the rotational motion of the translationally static sulphate ions. This is observed not only for the abundant cations, but also for other cations present (mono- as well as polyvalent) and for monovalent anions. Furthermore, both bulk diffusion and transfer along high diffusivity paths are affected. In addition, one can distinguish between different contributions to the bulk diffusion. The ionic radius is a very important parameter, since it determines the solid solubility and the distribution of the ions between the sites that are available in the lattice. All this affects the relative importance of several competing diffusion mechanisms. This gives a qualitative explanation of an anomalous correlation which has been observed in FCC Li₂SO₄ for monovalent ions (cations as well as anions), namely that both the diffusion coefficients D, and the activation energies Q, decrease when the radius is increased. This holds for hard-core cations (Li, Na, K, Rb), polarizable cations (Ag, Tl) and anions (F, Cl, Br). On the other hand, the situation is normal for divalent cations for which an increase in D corresponds to a decrease in Q. This is the case for hard-core ions (Mg, Ca) as well as for polarizable ones (Zn, Cd, Pb). Migration of the large ions Cs⁺ and SO²⁻₄ appears to be specially sensitive to how the experiment is prepared. Diffusion in BCC LiNaSO₄ and LiAgSO₄ has been studied for the two main cations as well as for some dopant ions. A general conclusion is that studies of diffusion of several ions in the same structure can give information that cannot be obtained by other types of experiments.     

Second-Stokes YVO4/Nd:YVO4/YVO4 self-frequency Raman laser

We demonstrated an efficient second-Stokes Raman laser emission at 1313 nm based on self-frequency stimulated Raman scattering from a diode-end-pumped actively Q-switched YVO(4)/Nd:YVO(4)/YVO(4) laser at 1064 nm for the first time, to the authors' knowledge. A double-end diffusion-bonded Nd:YVO(4) composite crystal was adopted for sufficiently improving the thermal lensing effect in the course of self-frequency stimulated Raman scattering operation. With an incident pump power of 14.6 W and a pulse repetition (PRR) of 40 kHz, a maximum average output power of 2.34 W was obtained, corresponding to an optical-to-optical conversion efficiency of 16%. Pulse width and peak power were 1.2 ns and 49 kW, respectively.     

The 4s~24p~3—4s4p~4 transition in Cd ⅩⅥ

The available experimental energies for the 4s~24p~3 and 4s~4p~4 configurations in As Ⅰ—like Sr Ⅵ—Ag Ⅹ Ⅴions are compared with the values calculated using the Hartree—Fock method including configuration interaction and relativistic corrections. Some energy values of the 4s~24p~3 configuration in Rh Ⅹ Ⅲ、Pd Ⅹ Ⅳ and Ag Ⅹ Ⅴ ions are improved and all the energies、wavelengths and transition probabilities of the 4s~24p~3—4s4p~4 transition array in Cd Ⅹ Ⅵ are presented.     

New Li+ ion conductors in the system Li4SiO4−Li3AsO4

In the system Li₄SiO₄-Li₃AsO₄, Li₄SiO₄ forms a short range of solid solutions containing up to 14 to 20% Li₃AsO ₄, depending on temperature, and γ-Li₃AsO₄ forms a more extensive range of solid solutions containing up to ≈55% Li₄SiO₄. The Li₄SiO₄-Li₃AsO₄ phase diagram has been determined and is of binary eutectic character. The ac conductivity of polycrystalline samples was measured over the range 0 to at least 300°C for nine different compositions. The two solid solution series have much higher conductivity than the pure end-members; maximum conductivity was observed in the γ-Li₃AsO₄ solid solutions containing ≈40 to 55% Li₄SiO₄, with values of $\text{≈2×10}{}^{\mathrm{?6}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 20°C rising to ≈0.02 Ω^?1 cm^?1 at 300°C. These values are comparable to those found in the system Li₄SiO₄-Li₃PO₄. The variation with composition of the Arrhenius prefactor and activation energy has been interpreted in terms of the mechanisms of conduction. Li₃AsO₄ is a poor conductor essentially because the number of mobile Li⁺ ions is very small. This number, and hence the conductivity, increases dramatically on forming solid solutions with Li₄SiO₄, by the creation of interstitial Li⁺ ions. At ≈40 to 55% Li₄SiO₄, the number of mobile Li⁺ ions appears to be optimised. An explanation for the change in activation energy of conduction at ≈290°C in Li₄SiO₄ and at higher temperatures in Li₄SiO₄ solid solutions is given in terms of order-disorder of the Li⁺ ions.     

Spin-polarized electronic band structures of the Fe4N-Co4N system

We have calculated spin-polarized electronic band structures of cubic antiperovskite metal nitrides (Fe₄N, Fe₃CoN, FeCo₃N and Co₄N) by the full-potential method with mixed basis augmented plane wave plus local orbitals. It was shown that FeCo₃N has an energy gap of 0.2 eV at the Fermi level in the up-spin band and hence its half-metallic behavior is expected.     

$$N^{3/4}$$ N 3 / 4 Law in the Cubic Lattice

Journal of Statistical Physics - We investigate the Edge-Isoperimetric Problem (EIP) for sets with n elements of the cubic lattice by emphasizing its relation with the emergence of the Wulff shape...     

Immiscibility in the NiFe2O4-NiCr2O4 spinel binary

The solid solution behavior of the Ni(Fe_1−nCr_n)₂O₄ spinel binary is investigated in the temperature range 400-1200 °C. Non-ideal solution behavior, as exhibited by non-linear changes in lattice parameter with changes in n, is observed in a series of single-phase solids air-cooled from 1200 °C. Air-annealing for 1 year at 600 °C resulted in partial phase separation in a spinel binary having n=0.5. Spinel crystals grown from NiO, Fe₂O₃ and Cr₂O₃ reactants, mixed to give NiCrFeO₄, by Ostwald ripening in a molten salt solvent, exhibited single-phase stability down to about 750 °C (the estimated consolute solution temperature, T_cs). A solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to n values of 0.2 and 0.7 at 300 °C. The extrapolated solvus is shown to be consistent with that predicted using a primitive regular solution model in which free energies of mixing are determined entirely from changes in configurational entropy at room temperature.