苯丙氨酸桥联金属双卟啉的诱导圆二色光谱研究

本文报道了邻位和对位桥联苯丙氨酸锌双卟啉的合成，考查了双卟啉的分子结构对诱导圆二色性的影响。结果表明，两个卟啉环之间的π－π堆积和手性激子偶合作用是影响此类双卟啉圆二色光谱的主要因素。     

Experimental evaluation of phonon–phason coupling in icosahedral quasicrystals

By measuring phonon strain introduced in crystal approximants, the sign and magnitude of the phonon–phason coupling constant have been evaluated for icosahedral quasicrystals of Mg–Ga–Al–Zn and Al–Cu–Fe systems. The evaluated coupling constants are approximately ?0.04μ and 0.004μ (μ?=?shear modulus) for the former and the latter, respectively. They are in good agreement with the results of a previously reported theoretical calculation. Possible effects of phonon–phason coupling on the onset of phasonic elastic instability in icosahedral quasicrystals are discussed.     

一种新型尾式卟啉的合成及其光电性质研究

合成了新型尾式5-(2-(α-咪唑基间甲基苯甲酰胺基)苯基)-10,15,20-三苯基卟啉(H2TPP-Bz Im)及其Fe、Co、Zn配合物,并用核磁、质谱、红外光谱、紫外-可见光谱等对其化合物进行了表征,通过紫外吸收、荧光分析、循环伏安法研究了化合物的光电性质。结果表明,与四苯基卟啉(H2TPP)相比,该尾式卟啉及其配合物的紫外和荧光光谱均出现较明显红移。Fe和Co卟啉的循环伏安曲线表明不仅发生了卟啉环上的氧化还原反应,还发生了金属离子的氧化还原反应。     

Fermion-boson coupling model (QCVM) applied to odd Zn isotopes

Low lying energy levels and transition probabilities of^63,65,67Zn are calculated in the Quasicluster-vibration model (QCVM). This model is an extension of the Clustervibration model (CVM) for three-particle-cluster vibration coupling. Instead of a three-particle cluster, now a one broken pair (number projected three quasiparticle) cluster is coupled to phonon states. It turns out that the sequence of isotopes may be described with one set of parameters, along the same line as previously used in the CVM. The resulting spectra and electromagnetic properties, for positive and negative parity states of odd Zn isotopes, compare with experimental data equally well as large shell-model calculations; this seems to justify the extension of the CVM to these nuclei with more than three particles or holes beyond a closed shell.     

三元硅化物CaAlSi的电-声子耦合和超导电性研究

应用全势线性缀加平面波方法计算新超导体CaAlSi的电子能带结构,用带心冻结声子法计算了声子频率及电声子耦合常数,并讨论了它们的超导电性.考虑到Al,Si原子分布的无序性和完全等价性,我们采用了双层超格子原胞模型,并考虑了低频B1g1声子频率的非谐性效应.由此计算得到稳定的低频B1g1声子频率为110cm-1,对超导电性有较大的贡献的Cad态电子与B1g1振动模式间的电声子耦合常数为0.37.我们的结果与用虚晶近似的结果是一致的.并证明CaAlSi的超导电性可由中等耦合的BCS理论来解释.     

铁基氟化物超导体SrFe_(1-x)Co_xAsF(x=0,0.125)声子特性的第一性原理计算研究

采用基于第一性原理的平面波赝势方法,计算了铁基氟化物及其钴掺杂超导体SrFe1-xCoxAsF(x=0,0.125)在四方非磁态与正交条纹反铁磁态下的声子谱(声子色散曲线、声子态密度)及电-声子耦合常数.计算发现:条纹反铁磁相互作用下的自旋-声子耦合效应强于电-声子耦合作用使声子谱的宽度减小;自旋效应使声子的有效质量增加导致条纹反铁磁态下Fe原子与As原子的耦合振动频率减小.另外,掺杂和自旋效应是提高电-声子耦合常数的两个有效方法,但计算所得超导转变温度远小于实验测量值,表明铁基超导电性非简单的电-声子耦合配对机理.     

Structure and superconductivity in the ternary silicide CaAlSi

Using the linear response-linearized Muffin-tin orbital (LR-LMTO) method, we study the electronic band structure, phonon spectra, electron-phonon coupling and superconductivity for c-axis ferromagnetic-like (F-like) and antiferromagnetic-like (AF-like) structures in ternary silicide CaAlSi. The following conclusions are drawn from our calculations. If Al and Si atoms are assumed to arrange along the c axis in an F-like long-range ordering (-Al-Al-Al-and-Si-Si-Si-), one could obtain the ultrasoft B_1g phonon mode and thus very strong electron-phonon coupling in CaAlSi. However, the appearance of imaginary frequency phonon modes indicates the instability of such a structure. For Al and Si atoms arranging along the c axis in an AF-like long-range ordering (-Al-Si-Al-), the calculated electron-phonon coupling constant is equal to 0.8 and the logarithmically averaged frequency is 146.8 K. This calculated result can correctly yield the superconducting transition temperature of CaAlSi by the standard BCS theory in the moderate electron-phonon coupling strength. We propose that an AF-like superlattice model for Al (or Si) atoms along the c direction may mediate the inconsistency estimated from theory and experiment, and explain the anomalous superconductivity in CaAlSi.      

First-Principles Theory of Muon and Muonium Trapping in the Protein Chain of Cytochrome c and Associated Hyperfine Interactions

The microscopic details of the electron transfer in cytochrome c (cyt c) are being investigated by the Muon Spin Relaxation (μSR) technique. We are using the Hartree–Fock Cluster Procedure to determine the most likely trapping sites for μ⁺ and muonium (Mu) in the protein chain, and have performed extensive calculations in single amino acid molecules of the protein chain of cyt c. The double-bonded oxygen atom of the carboxyl group was identified as the trapping site for both μ⁺ and Mu. Utilizing the wave functions we obtained from the Hartree–Fock calculations, we have determined the hyperfine field that the μ⁺ in Mu experiences while the latter is trapped at the oxygen. This revised version was published online in September 2006 with corrections to the Cover Date.     

Dumbbell rattling in thermoelectric zinc antimony

Inelastic neutron scattering measurements on thermoelectric Zn4Sb3 reveal a dominant soft local phonon mode at 5.3(1) meV. The form factor of this local mode is characteristic for dumbbells vibrating preferably along the dumbbell axis and can be related to a vibration of Sb dimers along the c axis. The Lorentzian width of the mode corresponds to short phonon lifetimes of 0.39(2) ps and yields an estimate of the thermal conductivity that agrees quantitatively with recent steady state measurements. Heat capacity measurements are consistent with an Einstein mode model describing the local Sb-dimer rattling mode with an Einstein temperature of 62(1) K. Our study suggests that soft localized phonon modes in crystalline solids are not restricted to cagelike structures and are likely to be a universal feature of good thermoelectric materials.     

Superconductivity in boron-doped diamond

Superconductivity of boron-doped diamond, reported recently at T(c)=4 K, is investigated exploiting its electronic and vibrational analogies to MgB2. The deformation potential of the hole states arising from the C-C bond-stretch mode is 60% larger than the corresponding quantity in MgB2 that drives its high T(c), leading to very large electron-phonon matrix elements. The calculated coupling strength lambda approximately 0.5 leads to T(c) in the 5-10 K range and makes phonon coupling the likely mechanism. Higher doping should increase T(c) somewhat, but the effects of three dimensionality primarily on the density of states keep doped diamond from having a T(c) closer to that of MgB2.     

多原子半无限晶体中表面极化子的内部激发态

研究多原子半无限晶体中电子与表面光学(SO)声子耦合强,而与体纵光学(LO)声子耦合弱的极化子的激发态性质.采用线性组合算符和幺正变换方法导出与SO声子耦合强而与LO声子耦合弱情形下极化子的基态能量、第一内部激发态能量和激发能量.结果表明,多原子半无限晶体中与SO声子耦合强,而与LO声子耦合弱的极化子的基态能量、第一内部激发态能量不仅包含不同支LO声子和不同支SO声子与电子耦合的能量,而且也包含不同支SO声子之间相互作用贡献的附加能量.激发能量与体纵光学声子无关.     

Strong-coupling theory for the superfluidity of Bose-Fermi mixtures

We develop a strong-coupling theory for the superfluidity of fermion pairing phase in a Bose-Fermi mixture. Dynamical screening, self-energy renormalization, and a pairing gap function are included self-consistently within the adiabatic limit (i.e., the phonon velocity is much smaller than the Fermi velocity). An analytical solution for the transition temperature (T(c)) is derived within reasonable approximations. Using typical parameters of a 40K-87Rb mixture, we find that the calculated T(c) is several times larger than that obtained in the weak coupling theory, and can be up to several percent of the Fermi temperature.     

NMR Spectroscopic Studies of β-Methyl-Pyridine Binding to Cytochrome C

The binding of β-methyl-pyridine (β-MePy) to horse heart ferricytochorme c (cyt c) was studied by two-Dimensional exchange spectroscopy. Kinetic and equilibrium data for β-MePy binding to cyt c have been determined. Some hyperfine shifted resonances of β-MePy-cyt c have been assigned. Differences between β-MePy-cyt c and pyridine bound cyt c (py-cyt c) have been disscussed.     

基于磁共振的胞浆中无标记酵母细胞色素c构象变化追踪

细胞色素c(cytochrome c,cyt c)是一个重要的多功能蛋白.在线粒体中,它作为载体传递电子.而在细胞质中,它可能会作为凋亡起始因子启动细胞凋亡程序.复杂的细胞质环境是否会对其构象产生影响,以及产生怎样的影响,目前仍然没有得到确证.本研究通过无标记的基于甲基的核磁共振（nuclear magnetic resonance,NMR）技术追踪了野生型酿酒酵母iso-1 cyt c在酵母细胞匀浆液中的构象变化.发现cyt c在细胞匀浆中至少存在4种不同的氧化态构象和1种还原态构象.而且随着时间的推进,不同构象之间发生转换.结果表明cyt c的构象会随环境改变,这可能与抵抗氧化应激相关.     

Mechanism of the size dependence of the superconducting transition of nanostructured Nb

A direct measurement of the superconducting energy gap by point contact spectroscopy in nanostructured Nb films shows that the gap decreases with a reduction in the average particle size. The superconducting T(c), obtained from transport and magnetic measurements, also decreases with size and scales with the energy gap. The size dependence of the superconducting properties in this intermediate coupling type II superconductor is therefore governed by changes in the electronic density of states rather than by phonon softening. Consistent with the Anderson criterion, no T(c) was observed for sizes below 8 nm.     

四-(二甲氨基苯基)卟啉及其金属配合物的合成及光谱性能研究

以丙酸、乙酸、硝基苯为溶剂一步法合成了四-(二甲氨基苯基)卟啉(T(DMAP)P),并采用氯仿-N,N二甲基甲酰胺为溶剂合成了其与Zn2+,Mn2+,Tb3+三种离子的配合物,考察了溶剂种类、温度、时间对反应的影响,探讨了卟啉与金属盐反应两者用量的最佳比例,在较温和条件下合成了卟啉金属配合物,避免了高温合成金属卟啉不稳定现象。利用元素分析,IR,UV-Vis等方法确定了目标化合物的组成和结构。考察了不同浓度及温度下卟啉配合物的电导率并计算了其摩尔电导率。实验结果发现,卟啉与铽离子配合物摩尔电导率远大于锌、锰配合物。实验研究了不同金属离子对反应的影响,重点考察了卟啉及其金属配合物的分子光谱性能的差异。与四苯基卟啉相比,T(DMAP)P及其金属配合物UV-Vis光谱均发生红移,探讨了该现象产生的原因。     

Superconductivity in heavy alkaline-Earth intercalated graphites

We report the discovery of superconductivity below 1.65(6) K in Sr-intercalated graphite SrC(6), by susceptibility and specific heat (C(p)) measurements. In comparison with CaC(6), we found that the anisotropy of the upper critical fields for SrC(6) is much reduced. The C(p) anomaly at T(c) is smaller than the BCS prediction, indicating an anisotropic superconducting gap for SrC6 similar to CaC6. The significantly lower T(c) of SrC(6) as compared to CaC(6) can be understood in terms of "negative" pressure effects, which decreases the electron-phonon coupling for both in-plane intercalant and the out-of-plane C phonon modes. We observed no superconductivity for BaC(6) down to 0.3 K.     

Intercalant and intermolecular phonon assisted superconductivity in K-doped picene

K(3) picene is a superconducting molecular crystal with a critical temperature of T(c) = 7 or 18 K, depending on the preparation conditions. Using density functional theory we show that electron-phonon interaction accounts for T(c) 3-8 K. The average electron-phonon coupling, calculated by including the phonon energy scale in the electron-phonon scattering, is λ = 0.73 and ω(log) = 18.0 meV. Intercalant and intermolecular phonon modes contribute substantially (40%) to λ as also shown by the isotope exponents of potassium (0.19) and carbon (0.31). The relevance of these modes makes superconductivity in K-doped picene peculiar and different from that of fullerenes.     

Spin-P honon Renormalization of the Excitation Energy in a Diluted Two-Dimensional Ferromagnet

The contribution of spin-lattice coupling to the phonon self-energy is calculated for a diluted two-dimensional "soft" ferromagnet. The calculations are based on a bond percolation model. Numerical results are presented for the dampings of phonon excitations. At low temperature, the damping rate is much smaller than the frequency of excitations, leading to well-defined phonons. The overall features of the Г ( q ) curves possess similar characteristics: Г ( q ) has two maximum points at qa ≈ 0.5 and qa ≈ 1.7, the value of the latter is much larger than the former. The temperature-dependent phonon line widths arising from spinlattice coupling are also presented. We point out the sensitivity of the interaction on bond concentration of the network.     

Cd_(0.96)Zn_(0.04)Te低温Raman光谱中荧光背景的猝灭现象

研究了Cd0 .96 Zn0 .0 4Te表面低温Raman散射光谱中的样品荧光背景随激光功率的变化行为 ,观察到了荧光的“猝灭”现象和同时伴随的声子峰红移 .分析表明样品荧光的“猝灭”现象与声子峰红移显示的表面结构变化有关 ,而激光对Cd0 .96 Zn0 .0 4Te表面的加热是导致表面晶体结构变化的原因 .