Vibrational relaxation in CD4 and CD4-rare gas mixtures

Using the optic-acoustic effect, measurements of the relaxation time were made after exciting the v₄ mode of CD₄. This was done for pure CD₄ and for mixtures of CD₄ with He, Ne, Ar and Kr, the results being 3.9±0.2, 1.8±0.2, 18±2, 70±15 and ? 100 μs at 1 atm, respectively. From the relaxation time dependence on mass as well as from a comparison between results for CH₄ and CD₄ it is concluded that energy transfer takes place via a vibration-rotation-translation (V-R-T) mechanism.Experiments were also conducted to study the most probable deexcitation path from the higher energy mode, v₃, to translation. This was done for CD₄-CD₄ as well as for CD₄-atom collisions. For pure CD₄ deexcitation occurs via the lower energy group (v₂, v₄), while for CD₄ mixtures it may also occur via the higher energy group (v₁, 2v₂, v₂ + v₄, 2v₄).     

Electron-driven processes for furan,tetrahydrofuran and 2, 5-dimethylfuran

We present the study of electron-induced processes for biomolecules, furan (C₄H₄O) and tetrahydrofuran (C₄H₈O) as well as an industrial relevant molecule 2, 5-dimethylfuran (C₆H₈O) through various total cross sections for impact energies from threshold to 5 keV. We have employed spherical complex optical potential to calculate total cross sections Q_T and total elastic cross sections Q_el. Since these molecules are complex molecules, we have used the group additivity rule which incorporates molecular properties as well as geometry of the target to evaluate these cross sections. Dependence of Q_T and Q_el on number of electrons and correlation of dipole polarisability (α) and ionisation potential (I) with peak of total ionisation cross sections Q_ion is studied and important inferences are noted. The present results for these applied molecules are compared with previous data wherever available. This is the maiden attempt to report Q_el and Q_T for 2, 5-dimethylfuran.     

Importance of pre-ionisation for the non-chain discharge-pumped HF laser

The importance of pre-ionisation for the non-chain discharge-pumped HF laser is studied through experiments on an X-ray photo-triggered laser using mixtures of Ne, SF₆, and ethane. The discharge dynamic in Ne/SF₆ mixtures or pure SF₆, as well as the stabilisation effect induced by C₂H₆ and consequences for the laser performance, are investigated for pre-ionisation electron density values, n_eo, ranging from 10⁶ cm^-3 up to 10⁹ cm^-3, as well as for the so-called discharge self-breakdown mode. Without ethane, the minimum n_eo value which is needed to complete 100% homogeneous charge deposition in the plasma is a very sharply increasing function of the SF₆ pressure. This hinders performance optimisation when the molecule used to react with F-atoms, for instance H₂, has no effect on the discharge dynamic. The minimum ethane partial pressure that is needed to stabilise the discharge depends on n_eo, the pumping pulse duration, the deposited electric charge, and the SF₆ pressure. Discharges in Ne/SF₆ can be much more efficiently stabilised by addition of a small amount of ethane than by an increase of n_eo. A pre-ionisation density as low as 10⁶ cm^-3 is sufficient to achieve the maximum laser energy value, but total suppression of the pre-ionisation has a detrimental effect on the active medium homogeneity. Received: 30 May 2000 / Revised version: 9 October 2000 / Published online: 9 February 2001     

Probing the isomer,fluorination and bond effects in C<Subscript>3</Subscript>H<Subscript>6</Subscript>, cyclo-C<Subscript>3</Subscript>H<Subscript>6</Subscript> and C<Subscript>3</Subscript>F<Subscript>6</Subscript> molecules using electron impact

We have carried out experimental and theoretical studies on electron scattering from the C₃H₆ isomers and C₃F₆ molecules and we report on total, differential as well as theoretical integral elastic cross-sections for these molecules. Vibrational excitation functions are also presented for the typical vibrational peaks in C₃H₆ and cyclo-C₃H₆ for the angle of 90^○, impact energy range of 1–16 eV and loss energies of 0.12 eV and 0.13 eV, respectively. In the cross-sections, clear differences in peak positions and magnitudes between the C₃H₆ isomers can be viewed as the isomer effect. The same is observed between C₃H₆ and C₃F₆ in a clear manifestation of the fluorination effect. The resemblance of the π^* shape resonance in the cross-sections, observed at about 2.2 eV for C₃H₆ and 3.5 eV for C₃F₆, to those in C₂H₄ and C₂F₄ clearly points to the effect of the double bond in the molecular structures for these molecules. Theoretical analysis is performed to provide rationales for the scattering dynamics.     

Specific heat of a Kondo superconductor: (La, Ce) Al2

The specific heat of LaAl₂ and (La_1-xCe_x)Al₂ (x ? 0.0064) has been measured between 0.3 and 5 K, both in the superconducting and in the normal state. For all samples the same values for the Debye temperature as well as for the electronic specific heat coefficient have been determined. LaAl₂ shows an excellent BCS behavior. A remarkable excess specific heat at low temperatures due to the Kondo effect has been observed for all superconducting as well as for the normal conducting (La_1-xCe_x) Al₂ alloys. The specific heat jump ΔC at T_c depressed rapidly with increasing Ce concentration, allows the Kondo temperature T_K ? 1 K to be determined. ΔC vanishes at finite temperatures.     

Resonance Raman excitation and electronic structure of the single bonded dimers (C ¯60)2 and (C 59N)2

Raman spectra are presented for the single bonded dimeric fullerene (C ₆₀ ^- ) ₂ and compared to optical spectra and Raman spectra of the isostructural and isoelectronic heterofullerene (C₅₉N)₂. The spectra of both materials exhibit strong correlations with respect to splitting, line position, and line intensity. This holds for non resonant excitation with blue and green lasers as well as for the strong resonances observed with red lasers. The latter observation is consistent with a downshift for the electronic transition energies as compared to C₆₀. The absorption edge of thin films of (C₅₉N)₂ was found at 1.4 eV. The three intercage modes were observed at 82, 103, and 111, and at 88, 98, and 106 cm^-1 for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. A surprising difference was found for the position of the pentagonal pinch modes in the two materials as they were observed at 1461 and at 1451 cm^-1, for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. This is interpreted as a consequence of some characteristic differences in the electronic structure of the two compounds. Received 25 January 2000 and Received in final form 10 April 2000     

Determination of isotropic and anisotropic knight shift in V3X compounds

Methods are described to determine the isotropic as well as the anisotropic part of the Knight shift from powdered samples of several V₃X compounds (V₃Co, V_77.5Ni_22.5, V₃Rh, V₃Pd, V₃Pt and V₃Ir). Measurements of the Knight shifts of the central line as well as the satellites prove to be necessary. The obtained values for K_iso are about 0.5% while K_ax is not larger than 0.03%.The influence of the X elements on the quadrupolar interaction frequency v_Q will be discussed.     

Molecular motion in liquid benzene by nuclear magnetic resonance

The proton spin-lattice relaxation time, T ₁, has been measured for a series of mixtures of benzene in perdeuterobenzene for the liquid in equilibrium with its vapour over the temperature range from below the normal freezing point up to the critical temperature. The two contributions to T ₁ due to interactions within the molecule (T _{1 intra}) and between molecules (T _{1 inter}) have been separated and are found to be very different in magnitude and in variation with temperature. The variation and magnitude of T _{1 inter} correlates well with other translational motion dependent properties such as self diffusion and viscosity. The correlation of T _{1 intra} with other re-orientation dependent properties such as deuteron T ₁ and Rayleigh scattering is poor.

The observed variation in T _{1 intra} and in particular the broad maximum at higher temperatures is then interpreted as due to a combination of dipolar and spin-rotation effects. This interpretation results in good agreement between the activation energies for re-orientational molecular motion deduced from proton T ₁ and deuteron T ₁. It supports the Hubbard theory for the relation between the dipolar and spin-rotation correlation times τ_d and τ_sr. It gives a rough value, 3·8 kc/s, for the spin-rotation interaction constant for protons in benzene. Reasonable values for τ_d and τ_sr are predicted and for all temperatures τ_sr < τ_d as expected.

There is clearly a considerable difference between the re-orientational and translational motion of the molecules in liquid benzene but the exact nature of the difference cannot be elucidated.     

Comparative analysis of the effect of La and Co on the superconductivity and energyband spectrum of YBa2Cu3Oy for different oxygen contents

Temperature dependences of the resistivity and Seebeck coefficient of Y(Ba_1−x La_x)₂Cu₃O_y and YBa₂Cu_3−x Co_xO_y samples (x=0–0.25) have been measured under maximum sample saturation with oxygen, as well as following their anneal in an oxygen-deficient atmosphere. The T _c (x) dependences for as-prepared samples were found to pass through a maximum at x=0.05, which persists after annealing for Y(Ba_1−xLa_x)₂Cu₃O_y and disappears for YBa₂Cu_3−x Co_xO_y. A phenomenological model of the band spectrum in normal phase has been used to determine the parameters of the conduction band and of the carrier system, and to analyze their variation with the dopant type and content, as well as with annealing. Despite the differences observed in the T _c (x) dependence, the critical temperatures for all the sample series studied were found to correlate with the conduction-band effective width. The mechanism of the effect of impurities on the band-structure parameters and the reasons for the different influence of annealing on the properties of Y(Ba_1−x La_x)₂Cu₃O_y and YBa₂Cu_3−x Co_xO_y are discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 389–394 (March 1997)     

High-resolution spectroscopy of CF2Cl2 in a molecular jet

Absorption spectra of CF₂Cl₂ were recorded around 923 cm^–1, with a resolution of 50 MHz. The application of the molecular jet technique considerably simplifies the spectra as compared to room-temperature experiments. Rotational and vibrational temperatures were measured for CF₂Cl₂ pure and seeded in Ar or He. Molecular constants were obtained for thev ₆ vibrational band of the two most abundant chlorine isotopic species, as well as vibrational band origines for thev ₆±v ₄ and thev ₆±v ₅ hot-bands of the CF₂ ³⁵Cl₂ isotope.Guest     

Phase monitoring during Nd15Fe77B8 preparation by the calciothermic reduction-diffusion process

We have examined the effect of various parameters involved in the preparation of the Nd₁₅Fe₇₇B₈ alloy by the calciothermic reduction-diffusion process. Both Nd₂O₃ and NdCl₃ were utilized as starting raw materials. Shorter reaction times and lower heating temperatures are required for the chloride than for the oxide. Among the characterization techniques used to evaluate the final product, Mössbauer spectroscopy was invaluable for the determination of the (Nd_1.1Fe₄B₄)/(Nd₂Fe₁₄B) ratio, which should be as low as possible.     

Pressure-broadened iodine-laser-amplifier kinetics and a comparison of diluent effectiveness

An iodine laser kinetic model is used to investigate inversion parameters in highly pressure-broadened amplifier systems using i-C₃F₇I as the parent compound and CO₂, N₂, He, Ne, Ar, Kr, and Xe as the diluent gas. These data are used to calculate a diluent merit function for diluent pressures P_d = 1–100 atm. The most effective choices for buffer gases are as follows: P_d ? 1 atm, CO₂; 1 atm ? P_d ? 10 atm, Ar; and P_d ? 10 atm, Ne.     

EXAFS study of local order in the amorphous chalcogenide semiconductor Ge2Sb2Te5

Studies of amorphous (a-) semiconductors have been driven by technological advances as well as fundamental theories. Observation of electrical switching, for example, fueled early interest in a-chalcogenides. More recently switching of the a-chalcogenide Ge₂Sb₂Te₅ has been applied quite successfully to DVD technology where the quest for the discovery of better-suited materials continues. Thus, switching provides researchers today with an active arena of technological as well as fundamental study. On the theoretical front, bond constraint theory — or BCT — provides a powerful framework for understanding the structure and properties of a-materials. Applications of BCT to switching in Ge₂Sb₂Te₅ holds the promise of finding the best composition suited for switching applications. This work presents EXAFS data that describe local bonding configurations in as-deposited Ge₂Sb₂Te₅. The data show that Ge₂Sb₂Te₅ may best be viewed as a random array of Ge₂Te₃ and Sb₂Te₃ structural units imbedded in a tissue of a-Te, 17% of which is over coordinated. In addition, a valence alternation pair defect is introduced to the model to satisfy charge conservation constraints.     

Electrical conductivity,diffusion of iron and the defect structure of α-Al2O3: Fe

A detailed defect model is developed for α-Al₂O₃:Fe accounting for conduction and diffusion at high temperatures as a function of iron concentration, oxygen pressure and temperature. This model involves single native and iron defects as well as triplets of (Fe_AlAl_iFe_Al), the latter dominating the defect structure at high Fe concentrations. Diffusion of Fe in A1₂O₃ is attributed to Fe_i^3.. The position of the Fe_Al' level is estimated.     

Crystal field and exchange interactions in rare earth transition metal salen compounds containing bipyridine, pyrazole complexes

Crystal field parameters for Pr³⁺ in {[Ni(salen)Pr-(hfac)₃](H₂O)} (noted as NiPr) and {[Ni(salen)Pr(hfac)₃(pyr)]-(CHCl₃)} (noted as NiPrpyr) have been found from a fit to the thermal variation in the magnetic susceptibility of NiPr and NiPrpyr. The nature of exchange interaction in [Cu(salen)Pr(hfac)3(pyr)] (noted as CuPrpyr), {[{Cu(salen)Pr(hfac)₃}₂(pyz)](H₂O)₃} (noted as Cu₂Pr₂pyz) and {[{Cu(salen)Pr(hfac)₃}₂(bpy)]-(CHCl₃)₂} (noted as Cu₂Pr₂bpy, bpy=4,4_-bipyridine) have been found using the derived results for NiPr and NiPrpyr. All the exchange interactions give significant contribution to the thermal variation in magnetic susceptibility below 50 K. The contribution due to Pr-Cu interaction is positive while that of the Cu-Cu and Pr-Pr interactions are negative. The behaviors below 10 K for Pr-Cu and Pr-Pr are difficult to explain, and point to a possible change in structure of CuPrpyr, Cu₂Pr₂pyz and Cu₂Pr₂bpy below 10 K. The theoretical thermal variations in the magnetic specific heat of NiPr and NiPrpyr are computed and discussed.     

A first-principles insight into Pd-doped MoSe2 monolayer: A toxic gas scavenger

Using first-principles theory, we investigate the Pd-doping effect on the geometric and electronic behaviors of MoSe₂ monolayer, and the adsorption behavior of Pd-MoSe₂ monolayer upon four toxic gases, namely NO, NO₂ SO₂ and H₂S. Desorption property of Pd-MoSe₂ monolayer upon four gases at diverse temperatures is analyzed as well to help explore its potential application. For Pd dopant adsorption onto MoSe₂ monolayer, somewhat n-type doping is determined, which accounts for the increased conductivity for intrinsic MoSe₂ monolayer. The strong adsorption ability and poor desorption performance of Pd-MoSe₂ monolayer upon four gases indicate its large potential as gas scavenger to remove these toxic gases from their surroundings. Moreover, it could be explored as a gas sensor for detection of NO, NO₂ and H₂S as well, given the obvious change in conductivity after gas adsorption based on band structure analysis. Our calculations would be beneficial to understand the TM doping effect on intrinsic MoSe₂ monolayer and to provide a first insight into the potential application as gas sensor or sweeper for Pd-MoSe₂ monolayer.     

Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

Concentration Fluorescence Quenching of L(-)-Tyrosine in Aqueous and Nonaqueous Solutions

Abstract

A number of studies have demonstrated the dependence of both the fluorescence lifetimes and quantum yields of tyrosine in solution upon the nature of the solvent as well as upon the absence or the presence of air in the tyrosine solutions employed. Photobleaching of tyrosine in vacuum at pH 6.1 was found to be practically zero, whereas exposure of tyrosine to the full light of a Hglamp for 10 to 20 minutes gave rise to formation of non-fluorescing photoproducts⁽¹⁾. In addition, the phosphorescence lifetimes of tyrosine were determined as 2.7⁺?0.2 sect 2.7⁺0.2 sec. and < 1 sec in 1% ETOH in aqueous solution and at pH 6.1 and pH 13, respectively(l). The very long phosphorescence lifetimes are definitely responsible to a considerable extent as far as photobleaching is concerned. However, the participation of the excited singlet state cannot be ruled out. In a review, the fluorescence lifetimes of tyrosine in queous solutions were found to vary between 2.6 nsec to 3.6 nsec⁽²⁾. On the other hand, the fluorescence quantum yields of tyrosine and various anologous compounds displayed a strong dependence upon the solvent. Such solvents used were water, n-butanol and p-dioxane. The following values of φ_fl were obtained: For p-HO-C₆H₄ -CH₂COOH; φ_fl=0.01, 0.22 and 0.34; for p-HO-C₆H₄-CH₃; φ_fl= 0.23, 0.39 and 0.45 and for p-HO-C₆H₄-CH₂CN; φ_fl =0.16, 0.34 and 0.34, respectively⁽³⁾. Furthermore, the value φ_fl of p-HO-C₆H₄-CH₂CH(NH⁺ ₃)C00^? in aqueous solutions was found to be 0.21, where- as that of p-HO-C₆H₄-CH²CH(NH⁺ ₃)COOH in similar solutions was 0.06. The fluorescence lifetime and quantum yield of phenol in Ethanol were found to be 4.7 nsec and 0.10, respectively⁽⁴⁾.     

激光诱导荧光法研究CH2Cl2分子的振动能量转移

本文中用激光诱导荧光法首次研究了有机分子CH₂Cl₂分子的振动能量转移。实验测得了CH₂Cl₂分子的ν₃和ν₃/ν₉振动模的激活和消激活速率常数,以及稀有气体分子对CH₂Cl₂分子的ν₃/ν₉振动模消激活的影响。用SSH理论计算了CH₂Cl₂-稀有气体碰撞,CH₂Cl₂分子ν₃/ν₉的V-T能量转移相对几率,分析讨论了CH₂Cl₂分子的振动能量转移的通道。 关键词：     

Nd2(Fe,Si)17合金的结构与磁性

本文对Nd-Fe-Si三元系富铁区域相的结构和磁性进行了研究。结果表明,Nd-Fe-Si三元系富铁区域(Fe>40at％),除出现NdFe₂Si₂三元金属间化合物外(Si>20at％),同时只出现Nd₂(Fe,Si)₁₇赝二元金属间化合物,其中Si取代9d位的Fe原子,而不能形成类似于Nd₂Fe₁₄B的三元金属间化合物,Si取代Nd₂Fe₁₇中的9d位Fe原子后,使晶胞体积缩小;使饱和磁化强度减小;同时使Fe次晶格的铁磁相互作用增强,导致居里温度增高;还使得Fe次晶格的易面各向异性减弱,造成室温下各向异性场减小。 关键词：