多重散射团簇方法对吸附系统SO2/Ag(110)的理论分析

利用多重散射团簇方法(MSC)对吸附系统SO₂/Ag(110)的S原子K边X射线吸收精细结构谱(NEXAFS)作了理论分析.研究表明,覆盖度为0.5时,吸附的SO₂的S—O键长比气体状态时增长了(0.014±0.006)nm,OSO键角减小了15°±5°;SO₂分子的S原子处于芯位,但两个O原子处于不对称的位置;分子平面与(110)的夹角约为52°,同时分子平面相对衬底表面法线有一小角度的倾斜.MSC计算证实了该吸附系统存在一介于π^{关键词： X射线吸收精细结构 2/Ag(110)')" href="#">吸附系统SO₂/Ag(110) 多重散射团簇方法}     

Infrared spectra of the matrix-isolated chlorides of iron,cobalt, and nickel

Iron, cobalt, and nickel metal cathodes were sputtered with various mixtures of ³⁷Cl₂/³⁵Cl₂/Ar to produce Ar matrices at 14 K that contained the mono-, di-, and trichlorides of the corresponding metal. The measured infrared absorption spectra of these matrices allowed the identification and characterization of FeCl₂, FeCl₃, CoCl, CoCl₂, CoCl₃, and NiCl₂. The derived vibrational constants of the electronic ground state of ⁵⁹Co³⁵Cl are ω_e = 457.8 ± 3.0 cm^?1 and ω_eχ_e = 2.0 ± 1.5 cm^?1. The antisymmetric stretching mode frequencies of six isotopomers of FeCl₂ and three isotopomers of CoCl₂ were identified and measured. The dichlorides of iron, cobalt, and nickel were all determined, in contrast with previous work, to be nonlinear with bond angles of 161, 157, and 161°, respectively. The estimated uncertainty is 5°. For both iron and cobalt trichlorides, the measured stretching mode frequencies were used to derive a ClMCl angle in excess of 120°, as would be expected for planar molecules with somewhat anharmonic vibrations. Observed adsorption peaks could be assigned to the ν₃(E) modes of planar (D_3h) Fe and Co trichlorides and the corresponding modes of the isotopomers. These observations strongly suggest that recent data supporting a pyramidal geometry for FeCl₃ should be reexamined. The geometry of CoCl₃ has not previously been determined.     

A facile synthesis about amorphous CoS<Subscript>2</Subscript> combined with first principle analysis for supercapacitor materials

The structure and electrochemical properties of amorphous CoS₂ and crystalline CoS₂ have been studied with both experimental characterization and theoretical calculations. In the field of experimental characterization, a facile chemical precipitation method is used to synthesize amorphous and crystalline CoS₂ samples with calcining temperatures of 200 and 280 °C, respectively. Comparing with crystalline CoS₂, amorphous structure of CoS₂ manifests great electron conductivity, effective porous structure, and exhibit a high specific capacitance of 996.16 F g^?1 at current density of 0.5 A g^?1, excellent rate capability of 89.8% retention with the current density ranging from 0.5 to 5 A g^?1, and a great cycling stability of 97.6% retention after 10,000 cycles at 2 A g^?1 in 6 mol L^?1 KOH aqueous electrolyte. In the area of theoretical calculation, we used the first principle and obtained the band structure with band gap of 0.00369 eV and DOSs with high locality of D-orbital from 69.88689 electrons/eV main peak, in the CoS₂ amorphous. The result confirms that amorphous CoS₂ have higher conductivity than crystalline CoS₂ in theory. In addition, the as-assembled asymmetric supercapacitor of Co-S-200//AC also exhibits the maximum specific capacitance of 104 F g^?1 within a cell voltage from 0 to 1.5 V at current density of 0.5 A g^?1 and indicates a great cycling stability of 95.68% and excellent capacitance behavior. All results demonstrate a great potential of amorphous CoS₂ active material for supercapacitors.     

Microwave spectrum,centrifugal distortion,substitution structure,and dipole moment of sulfine,CH2SO

The microwave spectrum of the reactive species sulfine (CH₂SO) has been studied. Assignments of 86 transitions of the ground vibrational state normal isotopic species, with J up to 60, have allowed a thorough centrifugal distortion analysis. With planarity implied by the I_c-I_a-I_b value of 0.1333 amu $\text{A}\text{?}{}^2$, spectral assignments of seven other isotopic modifications have resulted in the following substitution bond lengths and angles: CH_syn = 1.085 Å, CH_anti = 1.077 Å, CS = 1.610 Å, SO = 1.469 Å, ?HCH = 121.86^°, ?SCH_syn = 122.51^°, ?SCH_anti = 115.63^°, and ?CSO = 122.51^°. From Stark effect measurements of the normal and d₂ species, the dipole moment has been determined to be 2.994 D, oriented 25.50° relative to the SO bond and 9.61° relative to the normal species “a” axis. At an initial pressure of 30 mTorr in a clean brass waveguide, the lifetime of sulfine at 25°C is ～30 min.     

Spectre de photoélectrons et calcul des facteurs de franck-condon pour H2O,D2O,HDO

The first band of the photoelectron spectrum of HDO has been recorded. In agreement with the selection rules of the group theory, the fundamental terms of the three symmetric vibrations of HDO (C_s symmetry) have been observed. Taking the geometry of the ion as parameters, the Franck-Condon factors for the ionization of H₂O, D₂O and HDO have been calculated. The geometry of the H₂O⁺, D₂O⁺, HDO⁺ ions (ground state) have been determined accurately by comparison of the calculated results with the corresponding photoelectron spectra. This geometry is approximately the same for the three ions: r_OH  1,00 Å and < HOH  110°.     

Infra-red spectrum,structure and properties of the N2-Ar van der Waals molecule

The first spectroscopic observation of bound N₂-Ar van der Waals molecules has been achieved with a cryogenic long path cell maintained at 87 K. The infra-red spectrum exhibits prominent fine structure near the N₂ stretching frequency which is assigned to hindered internal rotation of N₂ within the weakly bound complex. An analysis of this fine structure yields a T-shaped equilibrium geometry in which the N₂ bond axis is perpendicular to the N₂-Ar van der Waals bond axis. The observed spectrum is shown to be consistent with an internal rotational barrier of 20 cm^-1 (57 cal/mole). Approximately 20 per cent of the bound species are trapped by this rotational barrier and acquire a locked semi-rigid structure. The remaining 80 per cent have ill-defined geometry and undergo hindered internal rotation. The rotational envelope of an infra-red fundamental is analysed to give an estimate of the N₂-Ar bond length as 3·9 Å.     

Structural studies of tetrachloride liquids

The differential cross-sections for neutron scattering from liquid carbon tetrachloride have been measured with the TSS instrument at the Harwell Electron Linac. Data were taken at seven different scattering angles for a wavelength range of 0·2–3·5 Å. The observed diffraction patterns at high momentum transfer (> 8–30 Å^-1) have been analysed in terms of the molecular form factor f ₁(Q). It was found that the oscillation amplitudes could be satisfactorily described only by introducing an energy-dependent term into the Debye-Waller factors of the form factor. The f ₁(Q) data were fitted with a four-parameter function for measurements at scattering angles of 150°, 90° and 58°. The carbon-chlorine bond length parameter was accurately defined in all cases and had a mean value of 1·766 ± 0·002 Å. The inclusion of an anharmonicity constant in the form factor gave an improved χ²-fit to the data with an increased value of 1·770 ± 0·002 Å for the bond length. The results are in excellent agreement with other measurements and show the importance of pulsed neutron techniques for molecular structure studies of disordered materials.     

Spectra and structure of organogermanes: Microwave and Raman spectra of methyltrichlorogermane

The microwave spectrum of methyltrichlorogermane has been investigated in the region 26.5 to 40.0 GHz. The ground state rotational constants, B, were found to be 1602.19, 1601.42, 1601.10, 1600.71, 1600.02, 1537.84, 1537.10, and 1536.36 MHz for the symmetric top molecules CH₃⁷⁰Ge³⁵Cl₃, CH₃⁷²Ge³⁵Cl₃, CH₃⁷³Ge³⁵Cl₃, CH₃⁷⁴Ge³⁵Cl₃, CH₃⁷⁶Ge³⁵Cl₃, CH₃⁷⁰Ge³⁷Cl₃, CH₃⁷²Ge³⁷Cl₃, and CH₃⁷⁴Ge³⁷Cl₃, respectively. For the asymmetric top molecules CH₃⁷²Ge³⁵Cl₂³⁷Cl and CH₃⁷⁴Ge³⁵Cl₂³⁷Cl the ground state rotational constants A, B, and C were found to be 1597.96, 1559.31, 1203 and 1597.17, 1558.59, 1207 MHz, respectively. From the rotational constants the r_s values for the GeCl bond distance of 2.135 ± 0.006 Å and the CGeCl bond angle of 106.0 ± 0.7° were obtained. The centrifugal distortion constant for the CH₃Ge³⁵Cl₃ species was calculated to be 0.35 ± 0.08 kHz. The Raman spectra of methyltrichlorogermane has been recorded in the gas phase and the methyl torsional overtone (Δν = 2) was observed. From the observed frequency shift the barrier to internal rotation has been calculated to be 1.45 kcal/mole.     

Microwave substitution structure of the amine group in Ortho-chloroaniline,C6H4CINH2

The microwave spectra of amine deuterated species of [2-³⁵Cl] and [2-³⁷-Cl]aniline, C₆H₄ClNH₂, have been observed. The rotators associated with the first two states of the amino group inversion have been assigned. A geometric structure has been calculated from the moments of inertia of all isotopic species in the ground state, indicating a small out-of-plane angle (34.5°), and a torsion around the CN bond of the NH₂ group. This deformation is explained by the formation of a hydrogen bond NH … Cl.     

过渡族元素掺杂BaTiO3-Tb1-xDyxFe2-y层状复合材料中的磁电效应

用溶胶-凝胶法制备1.0%mol Mn,Cr,Co掺杂 BaTiO₃(BTO)粉体,在1350℃下烧结成多晶陶瓷样品.X射线衍射和差示扫描量热分析表明,室温下掺杂BaTiO₃具有四方钙钛矿结构;居里点和相变潜热随Cr,Mn,Co掺杂逐渐降低.将掺杂BaTiO₃与Tb_1-xDy_xFe_2-y(TDF)胶合制成双层磁电复合材料,并研究了Cr:BTO-TDF,Mn∶BTO-TDF,Co:BTO-TDF层状复合材料中的磁电效应.实验表明,在340×80 A·m^-1偏置磁场下, Cr:BTO-TDF的横向磁电电压系数达到最大值586 mV·cm^-1·(80 A·m^-1)^-1.在400×80 A·m^-1偏置磁场下,Mn∶BTO-TDF和Co:BTO-TDF的横向磁电电压系数的最大值分别为480 mV·cm^-1·(80 A·m^-1)^-1和445mV·cm^-1·(80 A·m^-1)^-1.研究表明掺杂BaTiO₃-TDF层状复合材料中具有较强的磁电耦合.作为无铅压电材料,掺杂BaTiO₃制备的磁电效应器件颇具应用前景. 关键词： 磁电效应 双层复合材料 3')" href="#">掺杂BaTiO₃ 1-xDy_xFe_2-y')" href="#">Tb_1-xDy_xFe_2-y     

Thermal diffusion and the approach to the steady state in gases: II

The theory of the rate of approach to the steady state in themal diffusion is tested experimentally on the systems He-Ar, He-CO₂, H₂-CO₂, and D₂-CO₂ over a temperature range of about -78°c to 325°c. The course of the diffusion has been followed by means of the radioactive tracers ³⁷Ar and ¹⁴CO₂. The theory appears to be verified, and the results are used to calculate ordinary diffusion coefficients, which are in reasonable accord with previous measurements by other techniques. The thermal diffusion factors, which are obtained from the same measurements, also appear to have reasonable accuracy. The experimental method therefore appears to have promise as a sensitive method for the determination of forces between unlike molecules.     

Hierarchical porous ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> synthesized by the sucrose-assisted combustion method for high-rate supercapacitors

A simple sucrose-assisted combustion and subsequent high-temperature calcination route have been employed to prepare hierarchical porous ZnMn₂O₄ nanostructure. When used as an electrode for supercapacitor, the ZnMn₂O₄ electrode displays a high specific capacitance of 411.75 F g^?1 at a current density of 1 A g^?1, remarkable capacitance retention rate of 64.28 % at current density of 32 A g^?1 compared with 1 A g^?1, as well as excellent cycle stability (reversible capacity retention of 88.32 % after 4000 cycles). The outstanding electrochemical performances are mainly attributed to its hierarchical porous architecture, which provides large reaction surface area, fast ion and electron transfer, and good structure stability. All these impressive results demonstrate that ZnMn₂O₄ shows promise for its application in supercapacitors.     

A variational method for the calculation of spin-rovibronic energy levels of triatomic molecules with three interacting electronic states

A general method is presented for the evaluation of the spin rovibronic energy levels of triatomic molecules with up to three interacting potential energy surfaces. The full theory is outlined in detail, both for singlet and for doublet electronic states and the method is then applied to the benchmark example of C₂H. High quality multireference configuration interaction calculations have been carried out to generate the 3-dimensional near-equilibrium adiabatic potential energy surfaces of the three lowest 1²A'(X²Σ⁺), 2²A'(A²Π), 1²A''(A²Π) electronic states of C₂H, and the pair of interacting states of A 0 symmetry have then been diabatized. Results are presented for J up to 7/2 and compared with gas-phase high resolution experimental results for energies up to 5600 cm¹.     

Reflection measurements in CO2 laser solid deuterium target interaction

Using a 60 nsec, 300 MW CO₂ TEA laser reflection measurements from solid deuterium targets have been investigated. Energy, reflected and scattered pulse shape are recorded at various angles: 0°, 45°, 90°, 135°. Reflection, X-ray measurements and ion mean kinetic energy are correlated at the focussing lens position with respect to the target position. The maximum plasma temperature varies from 20 to 35 eV for incident laser fluxes ranging from 5 × 10¹⁰ up to 5 × 10¹¹ W/cm². The cut-off density inside the deuterium ice has been observed and located. In each case reflection has been found to be weak less than 5% for each direction. For the maximum fluxes X-ray energies greater than 0.5 keV have been observed.     

The structural and spectroscopic properties for uranium oxides

The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO 2 , UO 3 , and U 2 O 3 molecules are systematically investigated using the density functional theory (DFT) with the method of generalized gradient approximation (GGA). The bond lengths and the vibrational frequencies of the ground states of UO, UO 2 , and UO 3 molecules are all in agreement with available experimental data. For U 2 O 3 molecules, our calculations indicate that the ground state of the U 2 O 3 molecule is an X 7 A ′ 1 state with D 3h (trigonal bipyramid) symmetry (R 1 (U–O)=0.2113 nm, R 2 (U 1 –U 2 )=0.2921 nm, ∠U 1 OU 2 = 87.5 , dihedral angle Θ(U,O 1 ,O 2 ,O 3 )=62.40 ). The harmonic frequency, the IR intensity and the spin density of the U 2 O 3 molecule are all obtained for the first time in theory. For the ground state of U 2 O 3 molecules, the vibrational frequencies are 178.46 (A ′ 1 ), 276.79 (E ′′ 1 ), 310.77 (E ′ 1 ), 396.63 (A ′′ 2 ), 579.15 (E ′ 1 ), and 614.98 (A ′ 1 ) cm 1 . The vibrational modes corresponding to the IR maximum peaks are worked out for UO 3 and U 2 O 3 molecules. Besides, the results of Gophinatan–Jug bond order indicate that UO, UO 2 , and UO 3 molecules possess U=O double bonds and that the U 2 O 3 molecule possesses U–O single bonds and a U–U single bond.     

Die Eigenschwingungen des Metall-Hydratkomplexes in BeSO4·4H2O und BeSO4·4D2O

Infrared reflection spectra of single crystals of BeSO₄·4H₂O and BeSO₄·4D₂O have been obtained in polarized light at 300°K and at 14°K in the region between 4000 cm^?1 and 300 cm^?1. By a Kronig-Kramers analysis, the frequencies of the infrared active transitions have been calculated. These transitions are attributed to internal vibrations of the water molecules and sulfate ions and, in the region between 1000 cm^?1 and 300 cm^?1, especially to internal and external vibrations of the tetrahedral Be⁺⁺·4aqu-complexes. The vibrational modes of these complexes consist of a superposition of translational and librational modes of the water molecules and translational modes of the central Be⁺⁺-ion. The vibrational frequencies and normal modes of this complex have been calculated in a central-force model, and force-constants have been determined by fitting the calculated frequencies to the observed spectra. The calculations have shown that the modes, which comprise mainly translational motions of the water molecules, are strongly coupled with librational motions of the water molecules. On the other hand, there exist pure librational modes with practically no admixture of translational motions. The optimum sets of force constants for the BeSO₄·4H₂O crystal and the BeSO₄·4D₂O crystal differ in a manner which can be understood under the assumption that the dimensions of the Be(D₂O)₄ complex are about 0.1 Å larger than those of the Be(H₂O)₄ complex. Some arguments supporting this conclusion will be discussed.     

The geometry and forcefield of acetylene

The variational method has been used to determine the geometry and ground state potential surface of acetylene. All the parameters were refined through a least-squares fit to J = 0, 1 levels for C₂H₂ and C₂D₂. A new program was written to evaluate the rovibrational energy levels; in particular, primitive basis sets were developed for all values of J taking into account the singularity for linear geometries. Thus Σ, II, δ states can be refined. The full theory for tetraatomic linear molecules is presented. In this refinement 150 observed levels were used as data, below 10 000cm^?1. The geometry was refined and gives R_e(CC) = 1.2028 Å, R_e(CH) = 1.0618 Å, to be compared with the best experimentally derived values of 1.2027 ± 0.0005 Å, 1.062 ± 0.001 Å, respectively. The zero point energies are 5771.1cm^?1 for C₂H₂ and 4571.1cm^?1 for C₂D₂.     

Nematic-phase N.M.R. investigation of rotational isomerism: conformations of 2-furanaldehyde

An unrestricted Hartree-Fock molecular orbital procedure has been used to compute some properties of the lowest-lying spectroscopic states of NH₂, BH₂ and CH₂ ⁺. Computed bond angles for the ²B₁ and ²A₁ states of NH₂ and BH₂ are in good agreement with experimental data; bond lengths are about 6 per cent too great. Among other states for which predictions are made, the ²B₂ state of NH₂ has novel equilibrium geometry, with a predicted angle of 26·57°.

Dissociation products are considered. It is predicted that for the isoelectronic systems CH₂ ⁺ and BH₂ there is a contrast:

Other properties, such as isotropic coupling constants, force constants and dipole moments, are also reported.     

The N4 molecule and the N3 + ion

The possibility of the nitrogen molecule forming a stable dimer is investigated. Through ab initio calculations in an extended contracted-gaussian basis, it is demonstrated that N₄ in tetrahedral geometry and N₃ ⁺ in D _3h geometry are local minimum points on their respective internuclear potential energy surfaces. The N₄ molecule is considerably higher in energy than two ground-state N₂ molecules and some study of the barrier for N₄ decomposition has been made. The bond lengths and force constants for the two systems are shown to be similar to their hydrocarbon counterparts, C₄H₄ and C₃H₃ ⁺, tetrahedrane and cyclopropenyl cation. Other related systems are discussed as well.     

Alpha-heavy-ion angular correlations from 28Si + 12C

Alpha particles have been measured in coincidence with heavy recoil nuclei from the ²⁸Si + ¹²C reaction. At E_lab = 87 MeV angular correlations for alphas between 15° and 55° and heavy ions at angles ?9°, ?12° and ?15° have been taken. An excitation function of coincidence events with θ_α = 30° and θ_HI = ?12° has been measured for 84 MeV < E_lab < 91.5 MeV. The results are well described by a statistical-model calculation for compound nucleus decay. No evidence is found for additional processes.