氟化类金刚石薄膜的拉曼和红外光谱结构研究

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Possible spectroscopic manifestation of the angular group induced bond alteration (AGIBA) effect in toluene

The most obvious consequence of the concept of aromaticity is the common confidence that in aromatic compounds, bond lengths do not alternate and are between typical to the single and double ones. However, in 1994, performing crystal structure investigations of substituted pyridines and their salts, Krygowski and co‐workers have discovered a very surprising angular group induced bond alteration (AGIBA) effect: It appears that some angular substituents, like methoxy or nitrozo groups, can induce bond alternation in aromatic rings. Crystal studies do not allow one to operate with liquids that are more common in organic chemistry. This paper presents the first possible evidence of spectroscopic manifestations of the AGIBA effect. Raman spectra of the liquid toluene are analyzed. It is found that instead of being single, the line corresponding to the ring breathing vibrations is clearly split by 1.0–1.4 cm^?1, thus indicating the presence of two (cis‐ and trans‐) AGIBA isomers. The energy difference between these isomers estimated in temperature dependent Raman studies is found equal to 6.68 kJ mol^?1. The low‐wavenumber line therefore corresponds to the cis‐AGIBA isomer and the high‐wavenumber line to the trans‐AGIBA isomer stabilized by the AGIBA effect. Copyright © 2007 John Wiley & Sons, Ltd.     

Microsolvation of phthalocyanines in superfluid helium droplets.

Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule.     

Bohr-Mottelson转动谱公式参数之间的新关系式

在利用Harris两参数公式研究Bohr-Mottelson转动谱公式参数之间的关系的基础上,改用Harris三参数公式,并由此提出了Bohr-Mottelson转动谱公式参数之间的新关系式,进而用I(I+1)四参数展开式计算了A～60,80,130,140,150,190区超形变偶偶核的基带和锕系和稀土区正常形变核基带,讨论了参数之间的关系,发现新关系式与实验较好地符合.     

Zur Synthese von Bor-Schwefel(IV)-Stickstoff-Heterocyclen

Synthesis of Boron-Sulfur(IV)-Nitrogen Heterocycles The reaction of bis(lithio.tert.-butylamino)phenylborane with tert.-butyldichlorosulfimide and bischlorodimethylsilylsulfodiimide respectively leads to four- or eight-membered heterocycles. The disulfanebridge of one dithiazadiborolidine can be replaced by the ? N?S?N-sequence to yield a Thiatriazadiborine. ¹H, ¹¹B, ¹³C-NMR, mass spectra, and analytical data are reported and discussed.     

Liquid-phase chlorination ofC-chlorovinylsilanes

Liquid-phase chlorination of a number of chloro(chlorovinyl)methylsilanes was investigated. A number of novelC-chlorosilanes were characterized by IR and¹H NMR spectra. Some regularities of these reactions were determined; correlations between the structure of chloro(chlorovinyl)methylsilanes and their reactivities were identified.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2256–2260, November, 1995.     

锂锰尖晶石红外光谱的研究

本文对锂锰尖晶石的红外光谱进行了研究。由于锂锰尖晶石的晶体结构属于Fd3m空间群,锂离子占据四面体空隙(8a位置),锰离子占据八面体空隙(16d位置)。根据群论的知识,对锂锰尖晶石晶体中离子的振动方式与红外活性之间的内在关系进行了讨论。并列出了锂锰尖晶石的红外光谱实验数据。通过理论分析,我们推断:位于618.6和501.5cm~(-1)的红外吸收带分别来源于Mn(Ⅳ)-O和Mn(Ⅲ)-O键在晶体中的不对称伸缩振动(单元为Mn(Ⅳ)O_6和Mn(Ⅲ)O_6八面体),位于1124cm~(-1)的弱红外吸收带来源于Li-O键的不对称伸缩(单元为LiO_4四面体)。还有一些低于400cm~(-1)的可能吸收带在400～4000cm~(-1)范围内未能检测到。这一结论的可靠性通过锂锰尖晶石和掺杂的锂锰尖晶石的红外光谱实验数据得到证实。     

25MeV/u6He+9Be反应的轻粒子发射

在25MeV/u ⁶He与⁹Be靶的反应中,107°和128°处明显地观察到了轻粒子发射.粒子能谱形状与平衡热源蒸发相一致,分析得到热源的核温度为完全熔合条件下的5.6MeV或非完全熔合条件下的5.2MeV .实验发现发射氚的数量特别大,这可能与目前广泛研究的⁶He的集团结构和同位旋效应有关.     

用玻色子组态混合和玻色子表面δ相互作用研究核谱

用玻色子组态混合波函数和玻色子表面δ相互作用研究了三玻色子核⁴⁶Ti和⁵⁴Cr的sdgIBMI的能谱和E2跃迁概率,理论计算结果令人满意,比sdIBMI能拟合出更多的能级和E2跃迁概率,而且它们的误差更小. 说明g玻色子在振动区也起着重要的作用,同时进一步证明了这种玻色子组态混合模型是成功的.     

Time-resolved fluorescence study of the single tryptophan in thiocyanate and azide derivatives of horseradish peroxidase: Implication for a p H-induced conformational change in the heme cavity

Detailed pH-dependent steady state and picosecond time-resolved tryptophan fluorescence studies on thiocyanate and azide complexes of horseradish peroxidase have been carried out. The fluorescence decay of the single tryptophan in these species was fitted to a discrete three exponential model. Maximum entropy method analysis also gave three distinct regions of lifetime distributions. The fast subnanosecond lifetime component was found to have > 97% amplitude contribution while other two longer lifetime components have small contributions. Small contributions from the nanosecond lifetime components possibly arise from apoprotein impurity or some small amount of disordered heme conformer of the protein. pH dependence of the fast picosecond lifetime components was found to show a systematic behavior which has been interpreted in the light of obligatory conformation change associated with activation of the enzyme at low pH.