原子氧在Ru低指数面及(110),(111)台阶面上的吸附

利用原子与表面簇合物相互作用的5参数Morse势方法(简称5-MP)系统地研究了O-Ru低指数面及Ru(1120),(1121)台阶面体系,获得了吸附几何、结合能、振动频率等临界点特性,所得相关数据与实验结果非常吻合.并且通过理论计算及原子吸附态振动指纹的遗传、遗变特性预言了氧原子在Ru(1121)台阶面的吸附.本文认为氧原子在HCP晶格的金属表面上的吸附倾向于三重位.     

烷基极化效应与X=O键伸缩振动频率

烷基取代物R’X=0的X=0键伸缩振动频率ν与烷基R的极化效应指数PEI(R)的关系可表示为:ν=a bPEI(R)。研究结果表明,烷基的极化效应使X=0键的伸缩振动频率降低。     

Are the pyrazolines formed from the reaction of [60]fullerene with alkyl diazoacetates unstable?

[60]Fullerene-fused pyrazolines 1 were prepared by the reaction of C₆₀ with alky diazoacetates under the solid-state high-speed vibration milling conditions as well as in toluene solution. Pyrazolines 1 were stable in refluxing toluene and its thermolysis process in 1,2-dichlorobenzene was investigated, the decomposition rates and activation energies of pyrazolines 1 were obtained. The current work demonstrated that the liquid-phase reaction of C₆₀ with alkyl diazoacetates undergoes via 1,3-dipolar cycloaddition pathway at room temperature, or proceeds via carbene mechanism at a temperature of refluxing toluene, thus clarifies the previous ambiguity of its reaction mechanism.     

Analysis of the contribution of skeletal vibrations to the heat capacity of linear macromolecules in the solid state

Automatic computer programs are developed to calculate one- two-, and three-dimensional Debye functions. Prior tables of these functions are critically reviewed. Also, strategies are derived to calculate Debye temperatures from heat capacities. Both, simple three-dimensional Debye analyses and Tarasov analyses were carried out on 35 linear macromolecules. The experimental heat capacities for these analyses were collected in the ATHAS data bank. It is shown that the skeletal heat capacity of linear macromolecules is often best represented by only two vibrations per chain atom. For most of the all-carbon chain macromolecules the intramolecular skeletal heat capacity can be given by C_vs=D₁[520 (28/MW)^1/2] whereMW is the molecular mass andD ₁ represents the one-dimensional Debye function. Polyoxides show a higher intramolecular theta temperature, but a lower intermolecular theta temperature. Double bonds and phenylene groups in the chain increase the intramolecular theta temperature.Dedicated to Prof. Dr. F. H. Müller.On leave from the Lumumba Peoples' Friendship University, Moscow, USSR.     

Solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes under high-speed vibration milling

The solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes (RCHO) 2a-e under high-speed vibration milling (HSVM) conditions have been investigated. Fulleropyrrolidines 4a-e (C₆₀(CH₂N(CH₃)CHR), R=H (4a), C₆H₅ (4b), p-NO₂-C₆H₄ (4c), p-CH₃O-C₆H₄ (4d), p-(CH₃)₂N-C₆H₄ (4e)) were obtained in moderate yields from reactions of C₆₀ with aldehydes 2a-e and N-methylglycine (Prato reaction). In all these solvent-free reactions, 4a was found to be formed besides 4b-e, indicating that fullerenes can react with N-substituted glycines in the absence of aldehyde to give fulleropyrrolidines. For this novel reaction, a possible reaction mechanism involving an electron transfer process has been proposed. Intrigued by this observation, the dependence of the yield on the reagent ratio for the reaction of C₆₀ with paraformaldehyde and/or N-methylglycine was examined to search the optimal conditions. The reaction of C₇₀ with paraformaldehyde and/or N-methylglycine under HSVM conditions was also studied and was found to give the positional isomers of [70]fulleropyrrolidines.     

A vibrationally compensated far infrared laser interferometer for plasma density measurements

A modulated far-infrared laser interferometer which is presently operating on the PDX experiment at Princeton is described. The interferometer geometry permits the characterization of inside D, outside D as well as circular discharges. To achieve this versatility, a titanium corner cube reflector, mounted inside the PDX vacuum vessel is used in conjunction with a second visible wavelength interferometer for vibration corrections. In addition, the use of room temperature quasi-optical Schottky diodes in the far-infrared interferometer is reported. The minimum detectable line average density of the system is 5×10¹¹ cm^–3.     

Raman spectra and structural features of ClOF2 + cation in a solution of anhydrous HF

The Raman spectra of ClOF₂ ⁺ cation in solutions of anhydrous HF were studied. In the ClOF₂ ⁺HF₂ ⁻ and ClOF₂ ⁺BF₄ ⁻−HF systems, this cation exists as a pyramidal structure (C _s symmetry), while in the ClOF₂ ⁺AuF₆ ⁻−HF system, it exists as a planar structure (C _2v symmetry). Based on nonempirical calculations by the Hartree-Fock-Roothaan method, an explanation for the dependence of the structure of the ClOF₂ ⁺ cation on the nature of the anion was proposed. For the Cl−O bond vibrations, the correlation functions of vibrational and rotational relaxations were calculated, and the characteristic times of these processes were determined. The main contribution to the formation of the band contours corresponding to the above-mentioned modes is made by the vibrational dephasing. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 432–437, March, 1998.     

A new method for the derivation of exact vibration-rotational kinetic energy operator in internal coordinates

An efficient angular momentum method is presented and used to derive analytic expressions for the vibration-rotational kinetic energy operator of polyatomic molecules.The vibration-rotational kinetic energy operator is expressed in terms of the total angular momentum operator J,the angular momentum operator J and the momentum operator p conjugate to Z in the molecule-fixed frame Not only the method of derivation is simpler than that in the previous work,but also the expressions ot the kinetic energy operators arc more compact.Particularly,the operator is easily applied to different vibrational or rovibrational problems of the polyatomic molecules by variations of matrix elements Gn of a mass-dependent constant symmetric matrix     

Li-LSX沸石中阳离子分布与空分性能的研究

利用静态交换与动态柱交换的方法对低硅KNaX沸石进行Li~+交换．用XRD， ICP测定样品的晶相及化学红外光谱对LSX在Li~+交换中的骨架振动进行了研究．结 果表明：在Li~+交换过程中，谱峰的位移与本身性质有关，而且与LSX骨架中的离 子位置有关．还探讨了在高交换度的Li-LSX样品上的空分性能布的关系．     

Normal coordinate treatment of actinide(IV)-hexabromides

Molecular force field studies of hexabromo-thorates(IV) and-uranates(IV) have been carried out using four different force field models. Weighted least square adjustment has been used to fit the observed frequencies. Mean amplitudes of vibration have also been calculated at 0°K and 298°K. The trends of force constants and mean amplitudes have also been discussed.

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Normal-Koordinaten Berechnungen an Actiniden(IV)-hexabromiden

Zusammenfassung Es wurden für die Rechnungen an Hexabromo-thoraten(IV) und-uranaten(IV) vier verschiedene Modelle herangezogen. Die beobachteten Frequenzen wurden mittels gewichteter Kleinster-Fehlerquadrat-Methode angepaßt. Die Trends bei den Kraftkonstanten und den mittleren Amplituden der einzelnen Verbindungen werden diskutiert.