Al and Cu NMR study in UCu5Al

We have studied the microscopic properties of the tetragonal UCu₅Al Kondo compound by ²⁷Al and ^63,65Cu NMR in the paramagnetic state. NMR and susceptibility measurements performed on the powdered sample, but oriented along the applied field, showed χ>χ. Plots of K(T) against χ(T) at temperatures T≥100 K yield the transferred hyperfine fields of +5.9 kOe/μ_B for ²⁷Al nuclei, and +5.3 and −7.0 kOe/μ_B for ⁶⁵Cu nuclei in crystallographically inequivalent Cu(2) and Cu(1) sites, respectively. The Knight shift vs. susceptibility plots for T<100 K exhibit a deviation from the linear behaviour (absolute values of shifts become smaller than expected). We attribute this finding to the crystalline electric field effect in similar way as it was reported for several Ce-based compounds. The random distribution of the Al and Cu(2) atoms in the crystal lattice we consider as a reason of an unusual broadening of the NMR spectra, particularly at low temperatures.     

Substituent effect investigation of 3‐(2, 4‐dichlorophenyl)‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one. Part 1. Correlation analysis of 13C NMR chemical shifts

A series of substituted chlorinated chalcones namely, 3‐(2,4‐dichlorophenyl)‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one, have been synthesized, X being H, NH₂, OMe, Me, F, Cl, CO₂Et, CN, and NO₂. Dual substituent parameter (DSP) models of ¹³C NMR chemical shift (CS) have revealed that π‐polarization concept could be utilized to explain the reverse field effect at CO, the enhanced substituent field effect at CO, C‐2, and C‐5, and the decreased sensitivity of substituent field effect at C‐6. Chlorine atoms dipole direction at the benzylidene ring either enhances or reduces substituent effect depending on how they couple with the substituent dipole at the probe site. The correlation of ¹³C NMR CS of C‐2, C‐5, and C‐6 with σ and σ indicates that chlorine atoms in the benzylidine ring deplete the ring from charges. Both MSP of Hammett and DSP of Taft ¹³C NMR CS models give similar trends of substituent effects at C‐2, C‐5, and C‐6. However, the former fail to give a significant correlation for CO and C‐6 ¹³C NMR CS. MSP of σ_q and DSP of Taft and Reynolds models significantly correlated ¹³C NMR CS of C_β. MSP of σ_q fails to correlate C‐1′ ¹³C NMR CS. Investigation of ¹³C NMR CS of non‐chlorinated chalcones series: 3‐phenyl‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one has revealed similar trends of substituent effects as in the chlorinated chalcones series for C‐1′, CO, C_α, and C_β. In contrast, the substituent effect of the non‐chlorinated chalcone series at C‐2, C‐5, and C‐6 did not correlate with any substituent constant. Copyright © 2010 John Wiley & Sons, Ltd.     

新型萘酰亚胺衍生物的13C NMR研究

报道了四种新的萘酰亚胺衍生物的¹³C NMR谱. 应用¹H、¹³C、DEPT、HMQC、HMBC 等谱确定了这四种化合物的分子结构,并对全部谱峰进行了归属,探讨了分子结构对¹³C NMR化学位移的影响.     

稀磁半导体Zn1-xMnxTe吸收光谱压力红移的理论研究

以自由Mn²⁺离子的径向波函数为基础,通过引入电子云延伸效应系数κ来修正这一径向波函数,得到了稀磁半导体Zn_1-xMn_xTe晶体中Mn²⁺离子的径向波函数.以此波函数为基础,研究了Zn1-xMnxTe晶体吸收光谱的高压谱移特性,并且得到了吸收谱中四条谱线随压力的红移规律.     

拉盖尔-高斯光束在界面反射和折射的质心偏移特性研究

在圆柱坐标系中研究了傍轴线偏振拉盖尔-高斯光束在两种各向同性介质界面反射和折射后光强质心的偏移. 基于菲涅耳近似和泰勒级数展开,分别得到了部分反射和全反射两种情形下,质心的横向偏移和纵向偏移与光束拓扑荷的解析关系式. 研究表明,部分反射时,反射和折射光束的横向偏移的大小与光束的拓扑荷成正比,方向由拓扑荷的符号决定;而纵向偏移仅仅大小与光束的拓扑荷有关. 全反射时,反射光束质心偏移不受拓扑荷影响. 通过数值模拟验证了解析结果的正确性,并得到了解析公式的适用条件. 拉盖尔-高斯光束的质心偏移特性可应用于测量光 关键词： 拉盖尔-高斯光束 横向偏移 纵向偏移 拓扑荷     

Generation of large fifth-order nonlinear phase shifts by use of lossless χ(2) cascaded nonlinear processes

It is shown that the cascaded fifth-order nonlinear phase shifts will increase with energy loss in the cascaded processes. Essentially different from the multi-photon absorption accompanied with inherent material nonlinearities, the loss of fundamental wave in a cascaded process is controllable and suppressible. By introducing difference frequencies generated from the reaction between the fundamental and its second harmonic after the cascaded processes, the fundamental wave can be free of energy loss, while the large cascaded fifth-order nonlinear phase shift is maintained.     

大戟属植物中二萜酯和倍半萜甙结构的2D NMR研究

从阿勒颇侧大戟和巨枝大戟全草中分别得到的一个巨大戟烷型二萜酯和一个倍半萜甙，利用1H－1HCOSY；HMQC，RMBC等2DNMR技术归属了所有质子和碳的化学位移信号，并准确指定了二萜酯中每个酯基以及倍半萜甙中糖的连接位置．     

CO分子的A1Π(v=1)对d3∆(v=5)态的微扰研究

CO谱带的微扰给谱线的标识和分析带来挑战.这里针对CO A1Π(v=1)对d3∆(v=5)态的微扰,首先采用有效哈密顿矩阵的方法重新分析了d3∆—a3Π(5,0)带高精度的涉及d3∆2和d3∆3的振转光谱数据,发现A1Π的微扰可忽略不计.进一步理论计算了由A1Π的微扰产生的d3∆的∆1,∆2和∆3的转动能级移动和d3∆—a3Π(5,0)光谱强度的变化.发现∆1的能级移动最大,最大可达4 cm-1,这个能级移动随J值的增大而减小;对∆2和∆3的影响在J小时可忽略不计.光谱强度的改变有类似的变化趋势,涉及到∆1的d3∆1—a3Π光谱强度减小量最大可达20%,随J的增大,此减小量变小;对涉及∆2和∆3的光谱强度此微扰可忽略不计,从而给出了上面实验数据分析中不考虑微扰的原因.     

Line shape analysis of two-colour photoassociation spectra on the example of the Cs ground state

Two-photon photoassociation spectra in a Λ-type excitation scheme are analysed under the systematically varied experimental conditions of frequency detunings and laser intensities. Line shape fits are presented as well as the investigation of intensity and detuning dependent line shifts. From both we determine the attained spectroscopic precision, that is corrected for a systematic line shift due to the thermal distribution of atoms in the trap. An energy correction for this effect is given. Information about the feasibility of generating translationally cold molecules in a well defined rotational and vibrational level by the photoassociation process is derived from the analysis. Received 21 May 2002 Published online 15 October 2002 RID="a" ID="a"Current address e-mail: christian.lisdat@ptb.de RID="b" ID="b"e-mail: pierre.pillet@lac.u-psud.fr     

取代基对多取代氮苄叉苯胺化合物分子桥键（CH=N）的13C NMR和1H NMR的影响

Fifty-three samples of multi-substituted benzylideneanilines XArCH=NArYs (abbreviated XBAYs) were synthesized and their NMR spectra were determined. An extensional study of substituent effects on the ¹H NMR chemical shifts (^δH(CH=N)) and ¹³C NMR chemical shifts (^δC(CH=N)) of the CH=N bridging group from di-substituted to multi-substituted XBAYs was made based on a total of 182 samples of XBAYs, together with the NMR data of other 129 samples of di-substituted XBAYs quoted from literatures. The results show that the substituent specific cross-interaction effect parameter (Δ(Σσ)²)plays an important role in quantifying the ^δC(CH=N) values of XBAYs, but it is negligible for quantifying the ^δH(CH=N) values; the other substituent parameters also present different influences on the ^δC(CH=N) and ^δH(CH=N). On the whole, the contributions of X and Y to the ^δC(CH=N) of XBAYs are balanced, but the ^δH(CH=N) values of XBAYs mainly rely on the contributions of X.