K-Dependence and temperature dependence of N2-, H2-, and He-broadening coefficients for the J = 12-11 transition of acetonitrile CH3CN located near 220.7 GHz

Extensive experiments on the K = 3 component of the J = 12-11 rotational transition of acetonitrile CH₃C¹⁴N, located near 220.7 GHz, were performed at different temperatures in the range 235-350 K. They allow determining the N₂-, H₂-, and He-broadening coefficients, as well as their temperature dependences. More specific measurements on all the K-components of the involved transition perturbed by N₂ at 303 K allow to point out a clear decreasing of the broadening coefficient with increasing K. Narrowing effects are clearly observed, and experimental lines were analysed both with Voigt and speed dependent Voigt profiles; but no exhaustive lineshape study was carried out. All the experimental parameters are compared with results derived from a semiclassical calculation of collisional interactions, including electrostatic, induction, and dispersion energy contributions.     

Group algebras of Kleinian type and groups of units

The algebras of Kleinian type are finite-dimensional semisimple rational algebras A such that the group of units of an order in A is commensurable with a direct product of Kleinian groups. We classify the Schur algebras of Kleinian type and the group algebras of Kleinian type. As an application, we characterize the group rings RG, with R an order in a number field and G a finite group, such that the group of units of RG is virtually a direct product of free-by-free groups.     

希夫碱配合物的研究——Ⅵ.K[Fe(acaccn)(CN)2]·2H2O的合成及晶体结构

制备了K[Fe(acaccn)(CN)₂]·2H₂O.并测定了晶体结构.     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

A thermal and structural study on Lanthanum Hexacyanocobaltate(III) pentahydrate,La[Co(CN)6]·5H2O. Part III

On dehydration of La[Co(CN)₆]·5H₂O, the color of the complex, changes from white to pale blue at around 230°C. Heating the pale blue specimen, the color changes to deep blue at around 290°C. This deep blue specimen is easily rehydrated to a pink one. As reported previously, in the pale blue specimen, Co³⁺ ions are situated in the center of the D_4h crystal field formed by six CN^- ions. The deep blue specimen is due to the presence of [Co(CN)₄]^2- ions in which Co²⁺ was situated in a T_d coordination field formed by four CN^- ions and the Co-C bond length is 1.67 Ĺ. The pink species corresponded to trans-[Co(CN)₄(H₂O)₂]^2- and the bond lengths of Co-C and Co-O are 1.89 and 1.85 Ĺ, respectively. The Raman spectra of the complex observed at 25°C displays two bands at 2157 and 2176 cm^-1 associated with the vibration of C-N bond, and the band of 2157 cm^-1 was split into two bands, 2150 and 2156 cm^-1, at around 100°C. When the complex was heated to around 230°C, three new bands were observed at 2103, 2116 and 2141 cm-1. The bands of 2103 and 2116 cm^-1 were assigned to the stretching vibration of C=N bonding to Co²⁺. The band of 2141 cm^-1 was assigned to the stretching vibration of the inverted CN^- as follows: Co-C=N-La→Co-N=C-La. The activation energy for the inversion of CN^- was estimated as 67 kJ mol^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

配合物Cu(phen)2 (dca)2的合成及晶体结构

合成了配合物Cu(phen)2 (dca)2(phen=C12H8N2为1,10-邻菲啰啉,dca-为二氰基氨基阴离子),用IR对其结构进行了初步表征,并测定了配合物的晶体结构.该晶体属单斜晶系,空间群为P21/c;晶胞参数a=0.8869(2)nm,b=1.4691(2)nm,c=1.9298(2)nm,β=100.90(1)°;V=2.4691(8)nm3,Z=4,F(000)=1132.00,Dc=1.496g/cm3,R=0.051,RW=0.068.中心铜(Ⅱ)离子分别与两个phen中的四个N原子和两个dca-的两个N原子配位,形成六配位的变形八面体结构.     

直流放电制备CN自由基及其LIF探测

CN自由基是研究化学反应动力学的典型自由基，CN的动力学行为，如CN＋O2的反应已成为研究自由基－自由基反应的模型体系[1]，同时也在许多实际过程如燃烧过程，星际气体的形成过程中起着重要的作用[2，3]．利用含有CN的化合物进行光解、放电、与亚稳态原子分子进行传能反应是目     

H2O−D2O solvent isotope effect in the volume behavior of some high-charge high-size electrolytes

The apparent molar volumes V of KCl, BaCl₂, K₂SO₄, LaCl₃, Co(en)₃Cl₃ [Tris(ethylenediamine)cobalt(III) chloride], K₃Co(CN)₆, K₃Fe(CN)₆, K₄Fe(CN)₆, and Ba₃[Co(CN)₆]₂ have been determined at 25°C in both light and heavy water. The V values in D₂O are systematically lower and increase more rapidly with salt concentration than the V in H₂O. The volume of transfer from H₂O to D₂O as well as the partial molar volume at infinite dilution in both solvents have also been calculated. These results together with literature values for other electrolytes were used to estimate both of these quantities for D₂O solutions of individual ions. The predictions of ion hydration models and ion-ion interactions are compared with experimental observations.     

Solvent effects in a carbenoid N-H insertion route to triarylamines via 2-diazo-1,3-cyclohexanedione

The Rh-carbenoid derived from 2-diazo-1,3-cyclohexanedione inserts into the N-H bond of arylalkylamines and diarylamines. A solvent for this reactive carbenoid is suggested. The insertion products undergo a Pd-mediated aromatization to afford alkyldiarylamines and triarylamines.     

射频磁控溅射CNx薄膜的结构与衬底温度关系的研究

使用射频磁控溅射方法在不同衬底温度下（ts=室温，350，500℃）于Si(001)衬底上沉积了CNx膜，并利用拉曼（Raman)光谱、傅里叶变换红外光谱（FTIR）及X射线衍射光电子能谱（XPS）对CNx膜的化学结合状态与温度的关系进行了研究。Raman光谱结果表明，随衬底温度（ts) 增加，D带向低频方向移动，G带向高频方向移动；它们的半高宽分别由375和150cm^-1减小至328和142cm^-1；ID／IG由3．76减小至2.88。FTIR谱中除无序D带（1400cm^-1)和石墨G带（1570cm^-1)外，还有－700cm^-1,～2210cm^-1(C=N),2330cm^-1(C-O)及3255－3351cm^-1(N-H)等峰。XPS测试结果表明：随衬底温度增加，N与C的物质的量比由0.49下降至0.38，sp^2(C-N)组分与sp^3(C-N)组分强度比呈增大趋势。低温（350℃）退火并未对CNx膜的化学结合状态产生较大影响；高温（900℃）退火样品则显示出较好的结晶化程度。