Distinguishing between abstraction and addition as the first step in the reaction of a nitroxyl radical with cyclohexene

An unambiguous method for distinguishing between abstraction-addition and addition-abstraction mechanisms (and mixtures thereof) in the reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl with a specifically deuterated cyclohexene, 1,2-dideuteriocyclohexene, is demonstrated.     

青藏铁路多年冻土区工程复杂性分析

青藏铁路穿越550km多年冻土区,多年冻土地温、冻土类型以及沿线生态环境等存在较大的差异,使多年冻土区工程较为复杂。因此本文提出了冻土工程复杂性概念,建立冻土工程复杂性评价模型,并利用GIS平台对青藏铁路沿线唐古拉山越岭地段工程复杂性进行了分析和研究。研究结果表明,青藏铁路穿越的唐古拉山越岭地段工程复杂性相对较小,而青藏公路的工程复杂性相对较大。这表明了青藏公路沿线冻土工程比青藏铁路沿线更为复杂,在各种因素的影响下,青藏公路路基稳定性变化比青藏铁路更加复杂。     

The unexpected desulfurization of 4-aminothiophenols

Thermolysis of 4-aminophenyl benzyl sulfide at 523 K in the hydrogen donor solvent (HDS), 9,10-dihydroanthracene (AnH2), gave 4-aminothiophenol and toluene as the predominant products of the homolytic S-C bond cleavage. Under these conditions, a portion of the 4-aminothiophenol was desulfurized to aniline with first-order kinetics and with a rate constant estimated by kinetic modeling to be 7.0x10(-6) s-1. Starting with 4-NH2C6H4SH at 523 K, it was found that sulfur loss was more efficient in the non-HDSs, anthracene and hexadecane, than in AnH2. Under similar (competitive) reaction conditions, YC6H4SHs with Y=H, 4-CN, and 3-CF3 were completely inert; with Y=4-CH3O, there was some very minor desulfurization, whereas with Y=4-N(CH3)2 and 4-N(CH3)(H), the sulfur extrusions were as fast as that for Y=4-NH2. We tentatively suggest that this apparently novel reaction is a chain process initiated by the bimolecular formation of diatomic sulfur, S2, followed by a reversible addition of ground state, triplet 3S2 to the thiol sulfur atom, 4-NH2C6H4S upward arrow(SS upward arrow)H, and insertion into the S-H bond, 4-NH2C6H4SSSH. In a cascade of reactions, aniline and S8 are formed with the chains being terminated by reaction of 4-NH2C6H4S upward arrow(SS upward arrow)H with 4-NH2C6H4SH. Such a reaction mechanism is consistent with the first-order kinetics. That this reaction is primarily observed with 4-YC6H4SH having Y=N(CH3)2, N(CH3)(H), and NH2 is attributed to the fact that these compounds can exist as zwitterions.     

掺碲硒化镓晶体的光学性能(英文)

采用水平区熔法生长了碲(Te)掺杂浓度(质量百分比)分别为0.05%,0.1%,0.5%,1%,2%的硒化镓(GaSe)晶体,并分别对掺杂浓度为0.01%,0.07%,0.38%,0.67%,2.07%的GaSe∶Te晶体的光学性能进行了表征。首次研究了GaSe∶Te晶体中刚性层声子模式的转换。吸收光谱测试结果表明:当Te掺杂浓度小于0.38%时,振动中心位于0.59 THz附近的E'(2)刚性模式吸收峰强度可达最大值,这一过程与GaSe∶Te晶体光学性能的提高密切相关。但Te掺杂浓度的进一步提高会导致E'(2)刚性模式吸收峰强度逐渐减弱,当Te掺杂浓度为1%时,E'(2)刚性模式吸收峰基本消失。这两个过程与GaSe∶Te晶体光学质量的下降密切相关。因此,E'(2)刚性模式吸收强度达到最高时对应的掺杂浓度即是GaSe∶Te晶体中Te的最佳掺杂浓度,光整流产生太赫兹过程证实了此结论的正确性。     

An E.S.R. study of the structure of phosphorus centred radicals in solution

Clementi and Veillard's analysis of the MC SCF theory of closed-shell systems is developed on a different basis. An equivalent Hartree-Fock operator is defined and its physical significance is discussed. A generalized Brillouin theorem is derived, different from that given by Levy and Berthier.     

GaSe：AgGaSe_2晶体的光学性能及应用（英文）

从GaSe∶AgGaSe₂熔体(质量掺杂浓度为10%)中生长的非线性光学晶体ε-GaSe∶Ag晶体(质量掺杂浓度≤0.04%)是一种非中心对称晶体,可用于相位匹配频率转换。Ag的掺入使GaSe晶体的显微硬度提高了30%,从而使其可以在任意方向上进行切割和抛光。本文研究了GaSe∶AgGaSe₂晶体在可见、中红外及太赫兹波段的光学性能。实验证明:GaSe∶AgGaSe₂晶体的吸收系数是纯GaSe晶体的2倍,其CO₂激光倍频效率是ZnGeP₂晶体的1.7倍。     

Femtosecond dynamics of the collinear-to-spiral antiferromagnetic phase transition in CuO

We report on the ultrafast dynamics of magnetic order in a single crystal of CuO at a temperature of 207 K in response to strong optical excitation using femtosecond resonant x-ray diffraction. In the experiment, a femtosecond laser pulse induces a sudden, nonequilibrium increase in magnetic disorder. After a short delay ranging from 400 fs to 2 ps, we observe changes in the relative intensity of the magnetic ordering diffraction peaks that indicate a shift from a collinear commensurate phase to a spiral incommensurate phase. These results indicate that the ultimate speed for this antiferromagnetic reorientation transition in CuO is limited by the long-wavelength magnetic excitation connecting the two phases.