高压下L-丝氨酸的拉曼光谱研究

压力可以引起蛋白折叠与变性。作为蛋白质的基本构成单位,氨基酸在高压下的变化近来年备受关注。在常见的20种氨基酸中,学者们利用高压拉曼技术已研究了多种氨基酸在高压下的变化,研究的最高压力达到30 GPa。为了探究L-丝氨酸(C₃H₇NO₃)在极高压力下的结构变化情况,采用原位高压拉曼技术在常温下对L-丝氨酸晶体进行研究,最高压力达到22.6 GPa。研究发现,当压力达到2.7 GPa时,在102 cm-1处出现新峰,在1 123 cm-1(NH₃反对称摇摆振动)处的特征峰出现劈裂;当压力达到5.4 GPa时,L-丝氨酸晶体在574 cm-1处出现新峰,同时原来164 cm-1处峰消失;当压力达到6.0 GPa时,位于226,456,770和2 968 cm-1(CH₂伸缩振动)等处出现新峰,877 cm-1处的CC伸缩振动峰发生劈裂,产生894 cm-1新峰;当压力达到7.9 GPa时,在145,151和2 946 cm-1等出现新峰,同时原在CO₂摇摆振动峰的肩峰531 cm-1消失;当压力达到11.0 GPa时,位于249 cm-1处的振动峰开始劈叉,在241 cm-1处形成新峰,位于2 956 cm-1(CH₂伸缩振动)同时原位于391和431 cm-1处的峰消失;当压力达到17.5 GPa时,在200 cm-1处出现新峰。通过进一步分析L-丝氨酸的拉曼波数随压力的变化,发现很多拉曼峰在1.37,2.2,5.3,7.46和11.0 GPa以及15.5 GPa等压力点处都出现了拐点。其结果表明：L-丝氨酸在0.1～22.6 GPa之间共发生7处结构相变,分别位于压力区间0.1~1.37,2.2~2.7,5.3,6.0,7.46~7.9,10.1~11.0和15.5~17.5 GPa之间。而且,在6.0 GPa新的相变点在之前文献中未论述过。由于L-丝氨酸晶体在6.0 GPa时CC伸缩振动峰发生劈裂,这现象可能是由于压力引起L-丝氨酸晶体分子发生重排导致的,同时L-丝氨酸晶体分子重排导致氢键发生重排,使得L-丝氨酸晶体出现新的CH₂伸缩振动峰。L-丝氨酸晶体在10.1~11.0 GPa之间的拉曼光谱变化主要集中在低波数段,该波数段的拉曼振动模式主要与晶体晶格振动等低能量振动有关。同时在高波数段出现新的CH₂峰,由此可推测在10.1~11.0 GPa之间,L-丝氨酸晶体的晶格振动发生变化,产生了新的氢键,从而导致了L-丝氨酸晶体结构的改变。L-丝氨酸晶体在15.5~17.5 GPa之间,由于没有发现直接证据证明其发生结构相变,只是在拉曼波数随压力变化中,发现其在17.5 GPa时出现拐点,因此推测L-丝氨酸晶体在15.5~17.5 GPa之间可能发生结构相变。     

钽酸锂、蓝宝石在高压下的光学性质从头算研究

采用量子力学从头算和赝势平面波基组以及非局域广义梯度近似(PP-GGA)方法对两种光学窗口材料(单晶LiTaO3和蓝宝石α-Al2O3)在0~250 GPa静水压力范围内的光学透明性进行了研究.结果表明,随着压力的增加蓝宝石和钽酸锂的最大吸收峰位置均向低波长区移动(蓝移).蓝宝石在0~250 GPa压力下,可见光范围内一直保持其透明性,而LiTaO3则在高压下时就变得不透明了,其原因是钽酸锂的前沿能带闭合而导致其吸收带宽随外界压力的增大变宽所致.     

纳米晶类钙钛矿型锰氧化物导电性的高压研究

研究了纳米晶类钙钛矿型锰氧化物La0.7Sr0.3Mn0.95Fe0.05O3和La0.7Ca0.3MnO3在不同压力、高温处理后的导电性质.结果表明,在室温高压成型样品具有很高的电阻率,居里温度TC附近磁电阻效应很小 随处理压力的增加,电阻率先是降低,至11GPa时达最低点,之后升高.高温处理过的样品经一定压力处理后,其电阻随温度变化曲线的金属绝缘体转变峰向低温跃变,并伴随电阻率的大幅增加. 关键词：     

溴仿在冲击压缩下的光辐射及化学反应

 利用多通道光学高温计测量了溴仿在37 GPa到85 GPa压力范围内的温度,并观察了溴仿/单晶氯化钠界面的热驰豫过程。结果发现,当冲击波压力升高到46 GPa时,溴仿的光辐射强度随时间的变化呈现出“双阶梯”或“双台阶”形状的剖面结构,且台阶之间的时间间隔随冲击压力的增高而减小。当压力达到85 GPa时,上述“双台阶”结构消失,呈现为普通的单台阶剖面结构。冲击波温度测量表明,当压力低于50 GPa时,实测温度与Gokulya报道的数据一致;当压力增至76 GPa以上时,冲击波温度出现突跃性增加。结合对溴仿/氯化钠界面上的热驰豫过程的分析,文中提出,溴仿在上述冲击压力区间内发生了一次带有时间驰豫（或化学诱导期）的化学放热反应。     

钝感高能炸药三氨基三硝基苯高温高压下热力学性质的分子动力学模拟研究

热力学性质是钝感高能炸药1, 3, 5-三氨基-2, 4, 6-三硝基苯(TATB)爆轰性质和安全性评估分析的重要参数. 由于结构的复杂性, TATB炸药尚缺乏系统的实验和理论计算结果. 结合全原子力场和分子动力学的方法, 本文系统研究了不同温度和压力条件下TATB的力学性质和热力学参数, 得到了弹性模量、德拜温度等随温度、压力的变化情况, 并与实验进行了对比分析. 结果表明: 在 0-50 GPa外部压力下, TATB晶体保持力学稳定, 弹性常数和弹性模量随压力升高而增大, 各向异性程度随压力升高而减小, 泊松比和延展性则受压力的影响较小; 随温度的升高, TATB的力学稳定性逐渐下降, 有发生力学失稳的可能, 各弹性常数随温度升高而逐渐减小, 各向异性程度也随之减小; TATB 的声速和德拜温度同样随着压力升高而增大, 平均声速从0 GPa下的1833 m/s, 增加到10 GPa 下的3143 m/s, 德拜温度由0 GPa下的254 K增加到10 GPa的587 K. TATB 热膨胀系数的计算表明, 在200-500 K 温度常压情况下, 其体热膨胀系数为35.9×10^-5 K^-1, 与实验数据符合较好.     

冲击波诱导Nd_2Fe_(14)B磁相变的理论计算研究

根据Nd2Fe14B的冲击加载实验,计算了3.3—7.2 GPa压力范围内冲击波阵面上压力与温度的关系.基于分子场理论,引入压力等效场,改进了双亚点阵理论模型,并分析了在不同温度和压力下Nd2Fe14B的磁性转变机理.计算了压力对Nd2Fe14B磁致伸缩系数、磁化率、磁化强度以及居里温度的影响,给出了Nd2Fe14B发生铁磁–顺磁相变的压力和温度判据.计算结果表明:压力使Nd2Fe14B的居里温度逐渐向低温区转移,当压力从0 GPa增加到1.15 GPa时,居里温度从584 K降至292 K;随着压力的增加,Nd2Fe14B的磁化强度不断下降,且临界去磁压力随温度的升高呈下降趋势;在3.3—7.2 GPa压力范围内,Nd2Fe14B发生了铁磁-顺磁相变.     

量子点接触中的电导与热功率：磁场与温度的影响

在有限温度和不同磁场下，精确计算了各种鞍形量子点接触中的量子化电导和热功率.量子点接触的形状影响体系的量子化特征.随磁场的增加，量子化电导的台阶加宽，热功率共振峰之间的距离加长，共振峰的数量减少.当温度升高时，电导的量子化被破坏，热功率的峰状结构也逐渐消失. 关键词： 量子点接触 量子化电导 热功率 磁场     

PbMoO4原位高压拉曼光谱和电导率的研究

 钼酸铅（PbMoO₄）具有高的声光品质因数、低的声损耗、良好的声阻抗匹配等性质，被广泛应用于声光偏转器、调制器、可调滤光器、声表面波器件等各类声光器件，其优异的低温闪烁性能亦引起人们的注意，具有在核设备方面的应用潜力。为探讨其晶体结构和物理性质，在金刚石对顶砧上原位测量了PbMoO₄的拉曼光谱，并测量了其在几个不同压力点下电导率随温度的变化。实验发现，压力在12.5 GPa时，拉曼峰完全消失，说明压力在10.8～12.5 GPa之间PbMoO₄样品出现了非晶态转变。当从26.5 GPa卸压到9.4 GPa时，PbMoO₄的拉曼谱在低波数出现无序化，而在2.4 GPa压力下858 cm^-1峰又重新出现，说明样品结构由无序向晶化回复。压力在10.8 GPa以上时，电导率随着温度的增加而显著增加，且随着压力的增加也明显增加。     

La2/3Ca1/3Mn1-xCuxO3(x=0.15)系统低温下的电阻极小值现象及其起因

实验研究了La_2/3Ca_1/3Mn_1-xCu_xO₃(x=0和0.15)样品在温度远低于居里温度时的电阻随温度的变化行为.发现未加磁场时,Cu掺杂样品在低温下表现出电阻极小值行为.这一极小值现象在外加磁场后消失.基于Kondo理论,对实验观察进行了讨论,并作了定量的理论与实验的比较. 关键词：     

用超声方法研究掺丙氨酸氘化TGS晶体的相变

 采用超声脉冲重合技术，观察LADTGS在压力升至0.8 GPa，温度在20~90 ℃范围内，超声波在晶体中传播的速度及声衰减系数随温度变化的规律，发现在常压下，在64 ℃处声速随温度变化曲线的斜率有明显变化，对应的声衰减也有一明显吸收峰。随压力升高，T_c以约12 ℃/GPa的速率向高温方向移动。这一现象与介电常数的研究结果大致相同。     

High hydrostatic pressure effect on magnetic state of anion-deficient La0.70Sr0.30MnOx perovskite manganites

The magnetic state of La_0.70Sr_0.30MnO_x (x=2.85, 2.80) anion-deficient manganites is studied experimentally under hydrostatic pressure up to 5.2 GPa. These materials possessing the properties of a spin-glass state. The La_0.70Sr_0.30MnO_2.85 exhibits a coexistence of the rhombohedral (R3¯c) and tetragonal (I4/mcm) crystal structures and below T_f 50 K the spin-glass state is formed. The La_0.70Sr_0.30MnO_2.80 exhibits the tetragonal (I4/mcm) crystal structure. For this compound a phase-separated magnetic state below T_f is formed, involving coexistence of C-type antiferromagnetic (AFM) clusters within spin-glass matrix. In both compounds the crystal structure and magnetic states remain stable upon compression. Under the hydrostatic pressure up to 1 GPa, the La_0.70Sr_0.30MnO_2.85 is a spin glass with a smeared phase transition to the paramagnetic state. The freezing temperature T_f of the magnetic moments of the ferromagnetic clusters increases at a rate of 4.30 K/GPa and the magnetic ordering temperature T_MO increases at a rate of 12.90 K/GPa. The enhancement of the ferromagnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite under hydrostatic pressure is explained by the redistribution of oxygen vacancies and a decrease in the unit cell parameters.     

钙钛矿型锰氧化物(La$lt;sub$gt;0.8$lt;/sub$gt;Eu$lt;sub$gt;0.2$lt;/sub$gt;)$lt;sub$gt;4/3$lt;/sub$gt;Sr$lt;sub$gt;5/3$lt;/sub$gt;Mn$lt;sub$gt;2$lt;/sub$gt;O$lt;sub$gt;7$lt;/sub$gt;的磁性和电性研究

采用传统固相反应法制备钙钛矿型锰氧化物 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇多晶样品, X-射线衍射分析表明, 样品(La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇结构呈现良好的单相. 通过磁化强度随温度的变化曲线(M-T)、不同温度下磁化强度随磁场的变化曲线(M-H)和电子自旋共振谱发现: 在300 K以下, 随着温度的降低, 样品先后经历了二维短程铁磁有序转变 (T_C^2D ≈ 282 K)、三维长程铁磁有序转变(T_C^3D ≈ 259 K)、奈尔转变(T_N ≈ 208K)和电荷有序转变(T_CO ≈ 35 K); 样品 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇在T_N以下, 主要处于反铁磁态; 在T_C^3D达到370 K时, 样品处于铁磁-顺磁共存态, 在370 K以上时样品进入顺磁态. 此外, 分析电阻率随温度的变化曲线(ρ-T)得到: 样品在金属-绝缘转变温度(T_P ≈ 80 K)附近出现最大磁电阻值, 其位置远离T_C^3D, 表现出非本征磁电阻现象, 其磁电阻值约为61%. 在T_CO以下, 电阻率出现明显增长, 这是由于温度下降使原本在高温部分巡游的e_g电子开始自发局域化增强所致. 通过对 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇的ρ-T 曲线拟合, 发现样品在高温部分的导电方式基本遵循小极化子的导电方式. 关键词： 磁性 电性 金属-绝缘转变温度 电子自旋共振     

Evidence of new high-pressure magnetic phases in Fe–Pt Invar alloy

To investigate the magnetic properties of disordered Fe₇₀Pt₃₀ Invar alloy under high pressure, measurements of the real part of the AC susceptibility (χ) were made under pressure up to 7.5 GPa in the temperature range 4.2–385 K using a cubic anvil high-pressure apparatus. The Curie temperature (T_C) decreased with increasing pressure, and then, two new high-pressure magnetic phases appeared. These results show that the ferromagnetism of Fe–Pt Invar alloy becomes weaker, and the antiferromagnetic interaction becomes dominant with increasing pressure.     

The effect of annealing under hydrostatic pressure on the visible photoluminescence from si-ion implanted SiO2 films

We have studied the influence of the hydrostatic pressure during annealing on the intensity of the visible photoluminescence (PL) from thermally grown SiO₂ films irradiated with Si⁺ ions. Post-implantation anneals have been carried out in an Ar ambient at temperatures T_a of 400°C and 450°C for 10 h and 1130°C for 5 h at hydrostatic pressures of 1 bar–15 kbar. It has been found that the intensity of the 360, 460 and 600 nm PL peaks increases with rising hydrostatic pressure during low-temperature annealing. The intensity of the short-wavelength PL under conditions of hydrostatic pressure continues to rise even at T_a=1130°C. Increasing T_a leads to a shift in the PL spectra towards the ultraviolet range. The results obtained have been interpreted in terms of enhanced, pressure-mediated formation of ≡Si–Si≡ centres and small Si clusters within metastable regions of the ion-implanted SiO₂.     

Linear and nonlinear critical magnetic properties and transport in Nd0.75Ba0.25MnO3 single crystal: evidence for its anomalous critical behavior near TC

The data on the resistance and magnetoresistance (MR) as well as measurements of the linear and nonlinear susceptibilities are presented for a Nd_0.75Ba_0.25MnO₃ single crystal with the Curie temperature T_C≈129 K. Although this compound remains insulating in the ferromagnetic state, its resistance has an anomaly near T_C and it reveals the colossal magnetoresistance. The data on the magnetic response are well described by the dynamic scaling theory for 3D isotropic ferromagnets in the paramagnetic critical region at τ>τ^*≈0.11, τ=(T−T_C)/T_C. Below τ^* an anomalous critical behavior is found that suggests the coexistence of two magnetic phases. This behavior is discussed in terms of a phase separation which can occur in the moderately doped manganites exhibiting an orbital ordering.     

Evolution of superconductivity and charge order in pressurized RbV3Sb5

The kagome metals AV₃Sb₅(A=K,Rb,Cs)under ambient pressure exhibit an unusual charge order,from which superconductivity emerges.In this work,by applying hydrostatic pressure using a liquid pressure medium and carrying out electrical resistance measurements for RbV₃Sb₅,we find that the charge order becomes suppressed under a modest pressure pc(1.4 GPa3Sb₅.Our findings point to qualitatively similar temperature-pressure phase diagrams in KV₃Sb₅ and RbV₃Sb₅,{and suggest a close link}between the second superconducting dome and the high-pressure resistance anomalies.     

Effect of Yb addition on the superconducting properties of (Bi,Pb)-2212 superconductor

The effects of Yb addition on the phase evolution and superconducting properties of (Bi,Pb)-2212 superconductor prepared by solid state synthesis in the polycrystalline form were studied. Yb content of the samples was varied (x = 0–0.5) on a general stoichiometry of Bi_1.7Pb_0.4Sr_2.0Ca_1.1Cu_2.1Yb_xO_y. Phase analysis by XRD, microstructural examination by SEM, measurements of density and superconducting properties were done to evaluate the relative performance of the samples. A Yb containing secondary phase could be distinguished from XRD analysis from Yb > 0.3 in the stoichiometric level. Microstructural examination showed clear and distinct morphological variation with Yb stoichiometry and a secondary phase with round edged grains was observed in the microstructure of Yb added samples. The critical current density (J_C) and superconducting transition temperature (T_C) of all the Yb added samples were found to be higher than that of the pure sample. A maximum T_C-onset of 94.5 K and a maximum J_C 688 A/cm² has been observed for the sample with Yb = 0.2 in the stoichiometric level. Above this level T_C and J_C began to reduce, may be due to secondary phase formation.     

High pressure study on the superconducting transition temperature and Hall coefficient of Ba1−xKxBiO3 up to 8 GPa

The superconducting transition temperature (T_c) of Ba_0.62K_0.38Bio₃ (T_c=30 K) has been measured under high pressure up to 8 GPa. It is observed that T_c increases initially with pressure, as reported by Uwe et al., Shirber et al. and Huang et al., but decreases above 4 GPa. The Hall coefficient of Ba_0.62K_0.38BiO₃ has been measured up to 1.2 GPa. The absolute value of the Hall coefficient decreases with pressure by 10% GPa, the value of which is almost the same as that obtained in most CuO-based high-temperature superconductors.     

钙钛矿锰氧化物(La_(1-x)Eu_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.15)的磁性和电性研究

通过传统固相反应法制备了钙钛矿锰氧化物(La1-xEux)4/3Sr5/3Mn2O7(x=0,0.15)多晶样品,并且对其磁性和电性进行了研究.磁性测量表明:随着温度的降低,样品经历了一个复杂的转变过程,在温度为T*时经历二维短程铁磁有序转变,在温度为TC时进入三维长程铁磁态.随着Eu的掺杂,T*和TC减小,并且样品(La0.85Eu0.15)4/3Sr5/3Mn2O7在低温区表现出自旋玻璃行为.电性质测量表明:在母体La4/3Sr5/3Mn2O7中La位掺杂Eu后电阻率明显变大,金属绝缘转变温度TMI降低,磁电阻峰值增大.这些影响归因于较小的Eu3+离子替代La3+离子导致平均离子半径减小,晶格发生畸变.此外,较小的Eu3+离子优先占据层间岩盐层的R-site,使La3+,Sr3+,Eu3+离子在(La0.85Eu0.15)4/3Sr5/3Mn2O7中的分布更加有序,所以x=0.15的样品的ρ-T曲线只有一个峰.     

高压下NH_4ClO_4结构、电子及弹性性质的第一性原理研究

研究高压下NH_4ClO_4的结构和性质对于NH_4ClO_4在固体推进剂和炸药的安全应用具有重要意义.采用基于色散校正密度泛函理论的第一性原理方法,研究了0—15 GPa静水压力下NH_4ClO_4的晶体结构、分子结构、电子性质和弹性性质,计算结果与实验值具有较好的一致性.在压强为1,4和9 GPa时,NH_4ClO_4的晶体参数、键长和分子构型等均出现不连续变化,说明了在压强作用下结构发生变化.随着压强增加,氢键增多且作用增强,由分子内氢键向分子内和分子间的氢键转变;导带态密度峰值增加,电子局域性增强,晶体内N-H和Cl-O共价键作用增强,带隙增大,不同相变区域内带隙呈线性关系.0—15 GPa条件下NH_4ClO_4的弹性常数满足力学稳定性标准,采用Voigt-Reuss-Hill方法计算了体积模量B,剪切模量G和杨氏模量E,根据Cauchy压力和B/G值,说明NH_4ClO_4属于韧性材料,随着压强增加韧性增强.