The torsional-wagging tunneling problem and the torsional-wagging-rotational problem in methylamine

A theoretical formalism is presented for fitting rotational energy levels in isolated (unperturbed) vibrational states of methylamine. This formalism is obtained by recasting and extending theoretical studies in the earlier literature, which were undertaken to help analyze the methylamine microwave spectrum. The present formalism is applicable when both the NH₂ umbrella (wagging) motion and the CH₃ internal rotation (torsion) motion take place near the high-barrier limit and leads to the usual Fourier sine and cosine series expansions for molecular energy levels. The derivation is separated into two parts, one treating the large-amplitude vibrational problem (the torsional-wagging problem) by itself, the other treating the torsional-wagging-rotational problem. In both treatments, permutation-inversion group and extended group ideas are used to determine the allowed terms in an effective rotational-tunneling Hamiltonian operator and to block diagonalize the matrix representation of this operator for a near-prolate symmetric top. The resulting energy levels and selection rules are discussed, but application of the method in detail to the methylamine spectrum is planned for a later paper.     

The structure of liquid methylamine and solutions of lithium in methylamine

The technique of hydrogen/deuterium isotopic substitution in neutron diffraction has been used to measure the intra- and intermolecular correlations in liquid methylamine, and 2 and 8 MPM (mole percent metal) lithium methylamine solutions. We find that pure methylamine forms only one strong hydrogen bond per molecule, with evidence for weaker orientations towards the methyl group. As one introduces lithium metal, the intramolecular structure of the solvent is unaltered. However, intermolecular hydrogen bonding is progressively disrupted as the concentration of (solvated) cations and excess electrons increases. Comparison of the total structure factors for 0, 2, 8 and 20 MPM lithium methylamine solutions shows that the greatest shift in the position of the principal peak occurs between 8 and 20 MPM. This can be correlated to the electron delocalization associated with the non-metal-metal transition.     

甲胺分子的紫外光解离动力学实验研究

在280—287.5 nm区域内,通过实验测定共振增强多光子电离-时间飞行质谱、碎片离子的分质量激发谱以及光强指数等对甲胺分子的光解离通道进行了研究.实验结果证实甲胺分子在单光子能量范围内存在一个电子排斥态,主要的光解离过程为甲胺分子共振吸收1个光子到达该电子排斥态后解离成中性碎片,然后是中性碎片经多光子共振电离形成碎片离子和碎片离子的进一步解离.     

The rotational spectrum of the ground state of methylamine

Recent progress is reported in measuring, assigning, and fitting the rotational spectrum of the ground vibrational state of methylamine, CH₃NH₂, a spectrum complicated both by internal rotation of the methyl top and by inversion of the amino group. New measurements of 513 rotational transitions with J up to 30 and K up to 9 were carried out between 49 and 326 GHz using the millimeter-wave spectrometer in Kharkov. After removing the observed quadrupole hyperfine splittings, these new data along with previously published measurements were fitted to a group-theoretical high-barrier tunneling Hamiltonian from the literature, using 53 parameters to give an overall weighted standard deviation of 0.80 for 850 far-infrared and 673 microwave transitions in the ground state. The root-mean-square deviation of 0.018 MHz obtained for 346 millimeter-wave transitions measured with 0.020 MHz uncertainty represents an approximately 30-fold improvement in fitting accuracy over past attempts.     

Reaction pathway and H/D kinetic isotope effects of the triple proton transfer in a 7‐hydroxyquinoline‐methanol complex in the ground state: A computational approach

Multiple proton transfer (PT) is an essential process in long‐range proton transport such as proton relay in enzymes. 7‐Hydroxyquinoline (7HQ) undergoes alcohol‐mediated PT in both the excited and ground states, and this system has been investigated as a biomimetic model. In the present study, the reaction pathway of triple PT in a 7HQ‐methanol cluster, 7HQ·(MeOH)₂, in the ground state has been investigated using density functional theory calculations to clarify the reaction mechanism and the origin of the experimentally observed kinetic isotope effect (KIE). The PT takes place in an asynchronous concerted fashion, in which the oxygen atom in 7HQ first accepts a proton from the directly hydrogen‐bonded MeOH. The rate constants and primary H/D KIEs have been estimated with canonical variational transition state theory in combination with the small curvature tunneling approximation. The tunneling effect on the PT rate is significant, and the KIE is much greater than 1 at room temperature. The rule of the geometric mean for the KIEs breaks down because of the asynchronicity in the motions of 3 protons and tunneling effect. In addition, the rate constant is smaller, the KIE is larger, and the activation energy is higher compared with the experimental values in heptane solution, suggesting that the PT dynamics in solution is governed by not only the intrinsic PT process but also thermal fluctuation of the solute and solvent molecules, which plays an important role in the configurational change of the 7HQ·(MeOH)₂ complex.     

Photothermal waves for two temperature with a semiconducting medium under using a dual-phase-lag model and hydrostatic initial stress

The dual-phase-lag (DPL) model with two different time translations and Lord–Shulman (LS) theory with one relaxation time are applied to study the effect of hydrostatic initial stress on medium under the influence of two temperature parameter(a new model will be introduced using two temperature theory) and photothermal theory. We solved the thermal loading at the free surface in the semi-infinite semiconducting medium-coupled plasma waves with the effect of mechanical force during a photothermal process. The exact expressions of the considered variables are obtained using normal mode analysis also the two temperature coefficient ratios were obtained analytically. Numerical results for the field quantities are given in the physical domain and illustrated graphically under the effects of several parameters. Comparisons are made between the results of the two different models with and without two temperature parameter, and for two different values of the hydrostatic initial stress. A comparison is carried out between the considered variables as calculated from the generalized thermoelasticity based on the DPL model and the LS theory in the absence and presence of the thermoelastic and thermoelectric coupling parameters.     

Controlling morphology and structure of nanocrystalline cadmium sulfide (CdS) by tailoring solvothermal processing parameters

Cadmium sulfide (CdS) with different morphologies was successfully prepared by solvothermal process by controlling the processing parameters, including nature of precursor and solvent, reaction temperature and process time. X-ray diffraction patterns revealed that, in all cases highly pure and crystallized CdS with hexagonal structure were obtained. In addition, it was found that the processing parameters influence on preferable growth direction of CdS nanostructures. Field emission scanning electron microscope analysis showed that CdS nanowires with different aspect ratios were obtained (depending upon the reaction temperature and process time) in presence of sulfur powder and ethylenediamine, whereas CdS nanoparticles were produced by sulfur powder and ethanolamine. Moreover, CdS nanorods were prepared using thiourea and ethylenediamine. Transmission electron microscope image confirmed that CdS nanowire with one of the highest aspect ratio reported in the literature (i.e., 255) was achieved using sulfur powder and ethylenediamine at 200 °C reaction temperature for 72 h process time. UV–Vis absorption spectra of CdS nanostructures prepared under different conditions displayed a blue shift relative to that of bulk CdS due to the quantum size effect.     

The mechanism of aromatic nucleophilic substitution reaction between ethanolamine and fluoro‐nitrobenzenes: an investigation by kinetic measurements and DFT calculations

We have studied the kinetics and elucidated the mechanism by DFT calculation of the reaction between ethanolamine (EOA) and 1‐fluoro‐2,4‐dinitrobenzene (DNFB) in acetonitrile and toluene. To determine the contribution of the nitro group, the activation energy of the reaction between ethanolamine and 1‐fluoro‐2‐nitrobenzene (MNFB) vs. DNFB was determined in acetonitrile and calculated by DFT method. Kinetic measurements reveal that the reaction is faster in acetonitrile than in toluene. The reaction follows overall second‐order kinetics: first order with respect to both EOA and DNFB which is similar to the results reported for reaction between other primary amines and 1‐substituted‐2,4‐dinitrobenzenes. The calculations by using DFT methods reveal that the mechanism of the reaction involves the formation and decomposition of a Meisenheimer complex (MC). DFT calculations also reveal that the activation energy of the reaction is highest in vacuum and decreases with increasing polarity of the solvent reaching a minimum in acetonitrile. In addition, activation energies obtained by both DFT calculations and experiments show that the reactivity of MNFB is less than that of DNFB showing the effect of the 4‐nitro group. Copyright © 2010 John Wiley & Sons, Ltd.     

Reconceptualizing kinesin’s working cycle as separate chemical and mechanical processes

The biomolecular motor kinesin uses chemical energy released from a fuel reaction to generate directional movement and produce mechanical work. The underlying physical mechanism is not fully understood yet. To analyze the energetics of the motor, we reconceptualize its chemomechanical cycle in terms of separate fuel reaction and work production processes and introduce a thermodynamic constraint to optimize the cycle. The model predicts that the load dependences of the motor’s velocity, stepping ratio, and dwell time are determined by the mechanical parameters of the motor–track system rather than the fuel reaction rate. This behavior is verified using reported experimental data from wild-type and elongated kinesins. The fuel reaction and work production processes indicate that kinesin is driven by switching between two chemical states, probably following a general pattern for molecular motors. The comparison with experimental data indicates that the fuel reaction processes are close to adiabatic, which is important for efficient operation of the motor. The model also suggests that a soft, short neck linker is important for the motor to maintain its load transport velocity.     

Experimental characterisation, optimisation and design of erbium-doped silica fibre lasers

A new characterisation method is described using the new theoretical model for erbium-doped silica fibre lasers (EDSFLs) based on the energy conservation principle. Using this method, we obtained absorption and emission coefficients for the lasing wavelength at lasing operating conditions. After that, an experimental procedure to deduce the spectral profiles of the absorption and emission coefficients is also presented. This procedure allows us to obtain the values of these parameters for the whole fluorescence spectrum through measurements of gain profiles under the lasing operation. Once the absorption and emission coefficients are known, the new model can be applied and a comparison with experimental results for two different laser configurations is shown. The theoretical model is proved to be accurate and in addition some equations are developed to allow the design and optimisation of EDSFLs. This revised version was published online in March 2005. In the previous version, the published online date was missing     

Surface reconstruction in reactive dynamics: A kinetic Monte Carlo approach

The oscillatory CO oxidation reaction on the restructuring surface of Pt(1 0 0) is studied through a mesoscopic kinetic Monte Carlo (KMC) approach. The present model is an extension of the standard ZGB model with specific attention to the emergence of oscillations in surface reactions. A square and a purely hexagonal lattice are used as substrates on which the CO oxidation reaction steps take place. The dynamics of the reaction on the two substrates exhibit the ZGB kinetic phase transitions, at different kinetic parameter values for each substrate. Surface reconstruction is modelled through switching between the two lattice types. Oscillations are produced in those parametric areas where the steady state concentrations on the two substrates are considerably different. The parametric area where notable oscillations are observed is narrow, but is greatly enhanced when different sticking coefficients of oxygen are taken into account. CO diffusion introduced microscopically to the model on the hexagonal lattice shifts the kinetic transition points and increases considerably the time needed to reach the steady state.     

Calculation and analysis of cross-sections for p+~(184)W reactions up to 200 MeV

A set of optimal proton optical potential parameters for p+184W reactions are obtained at incident proton energy up to 250 MeV.Based on these parameters,the reaction cross-sections,elastic scattering angular distributions,energy spectra and double differential cross sections of proton-induced reactions on184W are calculated and analyzed by using theoretical models which integrate the optical model,distorted Born wave approximation theory,intranuclear cascade model,exciton model,Hauser-Feshbach theory and evaporation model.The calculated results are compared with existing experimental data and good agreement is achieved.     

Probing active site geometry using high pressure and secondary isotope effects in an enzyme-catalysed 'deep' H-tunnelling reaction

We report the first study of the effects of hydrostatic pressure on α-2° KIEs for an enzyme-catalysed H-transfer reaction that occurs by 'deep' tunnelling. High pressure causes a significant decrease in the observed α-2° KIE on the pre-steady-state hydride transfer from NADH to FMN in the flavoprotein morphinone reductase. We have recently shown that high pressure causes a reduction in macroscopic reaction barrier width for this reaction. Using DFT vibrational analysis of a simple active site model, we posit that the decrease in α-2° KIE with pressure may arise due to a decrease in the vibrational coupling between the NADH primary (transferred) and secondary hydrogens in the 'tunnelling ready configuration', which more closely resembles the reactant state than the transition state.     

CH自由基在外电场中的分子结构和势能函数

运用密度泛函B3P86方法,结合Dunning的相关一致五重基cc-PV5Z,获得了CH自由基分子在不同外电场中的键长、偶极矩和振动频率等物理性质参数.通过分析物理性质参数的变化,判断离解电场所处的范围,设置合适的参数扫描该范围的单点能获得势能曲线.结果表明物理性质参数和势能值随外电场的变化而变化,且反向电场中变化幅度较大.利用Morse势模型拟合无外场下势能函数,得到的拟合参数与实验值吻合较好,采用偶极近似构建外电场下的势能函数模型,编制程序拟合对应的势能函数,得出拟合参数,进而计算临界离解电场参量,结果与数值计算值较为一致,说明构建的模型是可靠和准确的.这为分析外场下分子光谱、动力学特性和分子Stark效应冷却囚禁提供重要的理论和实验参考.     

分形基底上刻蚀模型动力学标度行为的 数值模拟研究

为探讨分形基底结构对生长表面标度行为的影响, 本文采用Kinetic Monte Carlo(KMC)方法模拟了刻蚀模型(etching model)在谢尔宾斯基箭头和蟹状分形基底上刻蚀表面的动力学行为. 研究表明,在两种分形基底上的刻蚀模型都表现出很好的动力学标度行为, 并且满足Family-Vicsek标度规律. 虽然谢尔宾斯基箭头和蟹状分形基底的分形维数相同, 但模拟得到的标度指数却不同, 并且粗糙度指数 α与动力学指数z也不满足在欧几里得基底上成立的标度关系α+z=2. 由此可以看出, 标度指数不仅与基底的分形维数有关, 而且和分形基底的具体结构有关.     

Development of a hand-arm mechanical analogue for evaluating chipping hammer vibration emission values

This paper reports on the development and validation of a mechanical system designed to simulate the hand-arm dynamic response when coupled with a chipping hammer. The design is based on a two-degree-of-freedom lumped parameters model, in which the parameters are optimized such that the apparent mass of the mechanical analogue provides a close fit with the measured apparent mass of the hand-arm mechanical system. The apparent mass of the mechanical analogue has been validated on an electrodynamic shaker, than it was used to evaluate the vibration emission values of two different chipping hammers. Preliminary results show variations of <15 percent of the vibration emission values between human subjects and the hand-arm simulator for two different types of chipping hammers, while the variability in the results is found to be considerably reduced when using the mechanical analogue. The implementation of the mechanical analogue as part of a test set-up for the determination of the vibration emission values of chipping hammers is thus seen as an attractive alternative to the use of human subjects.     

Equivalence between local Fermi gas and shell models in inclusive muon capture from nuclei

Motivated by recent studies of inclusive neutrino nucleus processes and muon capture within a correlated local Fermi gas model (LFG), we discuss the relevance of nuclear finite-size effects in these reactions at low energy, in particular for muon capture. To disentangle these effects from others coming from the reaction dynamics we employ here a simple uncorrelated shell model that embodies the typical finite-size content of the problem. The integrated decay widths of muon atoms calculated with this shell model are then compared for several nuclei with those obtained within the uncorrelated LFG, using in both models exactly the same theoretical ingredients and parameters. We find that the two predictions are in quite good agreement, within 1-7%, when the shell model density and the correct energy balance is used as input in the LFG calculation. The present study indicates that, despite the low excitation energies involved in the reaction, integrated inclusive observables, like the total muon capture width, are quite independent of the fine details of the nuclear wave functions. An erratum to this article is available at .     

Microhardness and bulk modulus of binary tetrahedral semiconductors

Using the plasma oscillations theory of solids, the microhardness and bulk modulus of binary tetrahedral semiconductors have been calculated. New relations between plasmon energy and these parameters have been proposed. Our calculated values of microhardness and bulk modulus from two different equations are in excellent agreement with the experimental values and the values reported by other workers. In the present model, no experimental data are required except the plasmon energy, and one can predict the value of these parameters in the case of unknown semiconductors where experimental measurements have not yet been made due to a lack of availability of experimental melting points, dielectric constants or bond lengths.     

Computational study of cycloaddition reactions on the SiC(1 0 0)-c(2 × 2) surface

Cycloaddition reactions between 1,3-butadiene and the C-terminated SiC(1 0 0)-c(2 × 2) surface have been addressed using quantum-chemical methods. The c(2 × 2) structure consists of ---CC--- bridges between underlayer Si atoms which themselves form Si---Si bonds. Of various possible reaction products, the one formed by a [2 + 4] reaction with the ---CC--- bridge (giving a species resembling 1,4-cyclohexadiene) is the lowest in energy. Density functional calculations for the bare c(2 × 2) surface, using a cluster model with mechanical embedding, gave good agreement with structural parameters obtained in previous fully ab initio studies. Similar calculations for the cycloaddition product and for the transition state gave a reaction energy of −50.3 kcal/mol and an activation energy of +6.1 kcal/mol to form a planar ring structure lying normal to the surface. Detailed results for the frequency and infrared polarization behavior of adsorbate vibrational modes have also been obtained.     

霍尔推力器热模型研究

为了对霍尔推力器的热分析研究提供准确的能耗加载条件,开展了霍尔推力器稳态工况下的热模型研究。基于等离子体理论,分析放电室内各项能量损耗机理,并建立各能量损耗与推力器工作参数、性能参数和结构参数的相关函数,系统地得到了霍尔推力器的完整热模型。以LHT100推力器为研究对象,热模型计算结果显示:额定工况下束流能量损耗约889 W,壁面能量损耗约300 W,阳极能量损耗约44 W,电离能量损耗约43 W,辐射能量损耗约34 W等。以此能量损耗作为热边界条件进行有限元分析,并开展热平衡试验进行验证,计算结果与试验结果吻合较好,最大误差小于5%。