A theoretical study on calculation of ionic radii using limiting equivalent conductivities

Graphs of the total radius (the distance between an anionic nuclei and a cationic nuclei in a crystal) of sodium halides and alkali metal fluorides versus total limiting equivalent conductivities were plotted. For the hard ions Na⁺ and F⁻, whose behaviour approaches a hard spherical model, it was determined that radii values could be obtained using differences in limiting equivalent conductivities and ionic crystal data. From the determined radii of sodium and fluoride ions and known crystal data, radii of other alkali metal halides were calculated.

A molecular dynamics study of uranyl hydration

Molecular dynamics calculations were carried out in order to investigate the hydration structure of uranyl in aqueous solution. The CF1 model of flexible water molecules is used. This model allows one to investigate a hydrolysis reaction for water molecules in the first uranyl hydration shell. Charge redistribution effects on hydrolysis products are also taken into account. We found five ligands in uranyl hydration shell, which is of bipyramidal pentacoordinated structure. The charge redistribution effects resulted in ligands of four water molecules and one hydroxyl, which was found closer to uranium than the other ligands.     

A laser pistonphone based on self-mixing interferometry for the absolute calibration of measurement microphones

A laser pistonphone for the absolute calibration of microphones at low frequencies has been developed at UME. The motion of an electro-dynamically driven piston in a small close cavity produces a sound pressure. Accurate measurement of the piston displacement, by self-mixing interferometry, enables this sound pressure to be calculated, and consequently the pressure sensitivity of a microphone, exposed to this sound pressure, to be determined. Absolute calibrations of type LS1P and WS1P microphones have been carried out with an uncertainty of less than 0.15 dB. The performance of the laser pistonphone has been validated by comparing the measured microphone sensitivities with those obtained by the closed coupler reciprocity method.     

Comparative experimental study on absolute measurement of spherical surface with two-sphere method

The two-sphere method with multiple confocal measurements and a “cat's-eye” measurement is used widely in high accuracy interferometry, which can obtain the absolute surface data of the tested spherical surface. We provide a comparative experimental study on absolute testing procedures for spherical surface with two-sphere method, which include the classical Jensen method with three position measurements, the Zygo method with five position measurements and a variant of the Jensen method. The variant of the Jensen method can combine the multiple “three-position” measurements based on the fiducial method and averaging method. The repeatability of the involved absolute measurement methods is also studied by the five set experiments, and the corresponding Zernike fitting coefficients are compared in detail. The experimental results are meaningful for implementation of two-sphere method with higher repeatability in practice.     

A theoretical study of TeOH in its electronic ground state

The ab initio multireference single- and double-excitation configuration interaction (MRD-CI) method has been used to calculate the potential surfaces for the six lowest-lying electronic states of the TeOH molecule. The ²A″ ground state is predicted to have a bent equilibrium geometry. The first excited state, ²A′, is calculated to lie 2695 cm⁻¹ above the ground state. The MORBID program package has been used for the rotation-vibration analysis of the electronic ground state, for which the term values of the fundamental levels are calculated as 582 cm⁻¹ for the Te-O stretching mode, 959 cm⁻¹ for the bending mode, and 3655 cm⁻¹ for the O-H stretching mode.     

A theoretical study of some problems on low-noise pyroelectric detector-amplifier systems

The configurations of the coupling network, which can effectively aecrease the effect of the noise sources within the amplifier on the equivalent input noise of the whole pyroelectric detector-amplifier system, are studied. The influences of feedback upon the noise properties of the basic amplifiers are analyzed. The procedures of designing low-noise pyroelectric detector-amplifier systems are followed.     

A molecular dynamics study of the swelling patterns of Na/Cs-montmorillonites and the hydration of interlayer cations

We report on a molecular dynamics study of the swelling patterns of an Na-rich/Cs-poor montomorillonite and a Csmontomorillonite.The recently developed CLAYFF force field is used to predict the basal spacing as a function of the water content in the interlayer.The simulations reproduce the swelling patterns of the Na and Cs-montomorillonite,suggesting a mechanism of its hydration different from that of the montomorillonite.In addition,we find that the differences in size and hydration energy of Na and Cs ions have strong implications for the structure and the internal energy of interlayer water.In particular,our results indicate that the hydrate difference in the presence of coexistent Na and Cs has a larger influence on the behavior of a clay-water system.For Na-rich/Cs-poor montomorillonite,the hydration energy values of Na ions and water molecules each have a dramatic increase compared with those in Na-montomorillonite on the interlayer spacing,and the hydration energy values of Cs ions and water molecules decrease somewhat compared with those in Cs-montomorillonite.     

A theoretical study of FeCN in the Δ electronic ground state

The three-dimensional potential energy and dipole moment surfaces for the electronic ground state ⁶Δ of FeCN have been computed at the MR-SDCI + Q + E_rel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] level of theory, where MR-SDCI means ‘multi-reference single and double excitation configuration interaction’ and ANO means ‘atomic natural orbital’. Based on these potential energy and dipole moment surfaces, the spectroscopic parameters, rovibronic energies, structural parameters, vibrational transition moments, and the wavenumbers and intensities of selected rotation-vibration transitions have been calculated. The equilibrium structure is linear with r_e(Fe-C) = 2.048 Å and r_e(C-N) = 1.168 Å, and the zero-point averaged structure is bent with 〈r(Fe-C)〉₀ = 2.082 Å, 〈r(C-N)〉₀ = 1.172 Å, and 〈∠(Fe-C-N)〉₀ = 170(5)°. At all the MR-SDCI + Q and the size-extensive multi-reference averaged quadratic coupled-cluster (MR-AQCC) levels of theory, with and without relativistic correction E_rel, that were employed in the present work, ⁶Δ FeCN is predicted to be slightly more stable than ⁶Δ FeNC. For example, the energy difference between the two isomers is approximately 150 cm⁻¹ at the highest level of theory employed, MR-AQCC + E_rel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] with zero-point energy correction. The electronic structure of ⁶Δ FeCN has also been compared with that of ⁶Δ FeNC. At present, no experimental spectroscopic data are available for ⁶Δ FeCN. It is hoped that the present work will stimulate experimental investigations of this molecule.     

Theoretical ROVibrational Energies (TROVE): A robust numerical approach to the calculation of rovibrational energies for polyatomic molecules

We present a new computational method with associated computer program TROVE (Theoretical ROVibrational Energies) to perform variational calculations of rovibrational energies for general polyatomic molecules of arbitrary structure in isolated electronic states. The (approximate) nuclear kinetic energy operator is represented as an expansion in terms of internal coordinates. The main feature of the computational scheme is a numerical construction of the kinetic energy operator, which is an integral part of the computation process. Thus the scheme is self-contained, i.e., it requires no analytical pre-derivation of the kinetic energy operator. It is also general, since it can be used in connection with any internal coordinates. The method represents an extension of our model for pyramidal XY₃ molecules reported previously [S.N. Yurchenko, M. Carvajal, P. Jensen, H. Lin, J.J. Zheng, W. Thiel, Mol. Phys. 103 (2005) 359]. Non-rigid molecules are treated in the Hougen-Bunker-Johns approach [J.T. Hougen, P.R. Bunker, J.W.C. Johns, J. Mol. Spectrosc. 34 (1970) 136]. In this case, the variational calculations employ a numerical finite basis representation for the large-amplitude motion using basis functions that are generated by Numerov-Cooley integration of the appropriate one-dimensional Schrödinger equation.     

The theoretical calculation of transition probabilities for some excited p-d transitions in atomic nitrogen

The atomic transition probabilities are calculated for individual lines between some quartet terms of 3p↦4d and 3p↦5d transition arrays using weakest bound electron potential model theory (WBEPMT). In the determination of relevant parameters which are needed for calculation of transition probabilities, we employed numerical non-relativistic Hartree-Fock wave functions for expectation values of radius in both ground and excited states unlike to NCA method used on traditional WBEPMT procedure. We have obtained very good agreement between our results and the accepted values taken from NIST.     

From direct to absolute mass measurements: A study of the accuracy of ISOLTRAP

For a detailed study of the accuracy of the Penning trap mass spectrometer ISOLTRAP all expected sources of uncertainty were investigated with respect to their contributions to the uncertainty of the final result. In the course of these investigations, cross-reference measurements with singly charged carbon clusters ¹²C⁺ _n were carried out. The carbon cluster ions were produced by use of laser-induced desorption, fragmentation, and ionization of C₆₀ fullerenes and injected into and stored in the Penning trap system. The comparison of the cyclotron frequencies of different carbon clusters has provided detailed insight into the residual systematic uncertainty of ISOLTRAP and yielded a value of 8×10^-9. This also represents the current limit of mass accuracy of the apparatus. Since the unified atomic mass unit is defined as 1/12 of the mass of the ¹²C atom, it will be possible to carry out absolute mass measurements with ISOLTRAP in the future. Received 7 June 2002 Published online 6 November 2002 RID="a" ID="a"e-mail: a.kellerbauer@cern.ch RID="b" ID="b"Current address: Centre de Physique des Particules de Marseille, 13288 Marseille Cedex 9, France.     

A study on LiBOB-based nanocomposite gel polymer electrolytes (NCGPE) for Lithium-ion batteries

Lithium bis(oxalato)borate (LiBOB) salt-based nanocomposite gel polymer blend electrolyte (PVdF/PVC) membranes have been prepared by solution casting technique for various concentrations of TiO₂. The effect of anatase structure of nanosized titanium dioxide in the plasticized PVC/PVdF + LiBOB matrix has been observed in the 2:1 salt filler ratio in the impedance measurements that the conductivity is increased one order of magnitude higher than the filler-free electrolyte (1:0 salt:filler ratio). The phase morphology of this electrolyte membrane represents the appearance of the free volume sites for ionic migration.     

Influence of Ni and N on generalized stacking-fault energies in Fe-Cr-Ni alloy: A first principle study

The alloying effects of Ni and N were examined in terms of the generalized stacking-fault (SF) energy (GSFE). GSFE is associated with the basal plane of Fe-Cr-Ni austenitic stainless steel. The GSFE profiles were obtained using first-principle calculations. The results show that Ni increases the intrinsic SF energy γ_isf and the unstable SF energy γ_us. N does the opposite. However, a γ_isf/γ_us ratio close to zero accompanies the addition of Ni or N. This ratio implies that deformation by partial dislocation is preferred. Overall, the effect of N on Fe-Cr-Ni alloys is more evident than that of Ni.     

CO adsorption energies on metals with correction for high coordination adsorption sites - A density functional study

We investigate the accuracy of carbon monoxide adsorption energies and site preferences for the metals Ag, Al, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Re, Rh, Ru, W, and Zn using the RPBE functional with a recently suggested empirical adsorption energy correction for carbon monoxide based on the internal CO stretch vibrational frequency. We find that when including the correction, the adsorption site preference for six of the metals changes, and all adsorption site predictions become accurate. We also collect a large number of experimental studies for comparison with our calculated adsorption energies. The mean absolute deviation including the correction is found to be less than 0.2 eV, showing that the RPBE functional gives a much better quantitative agreement between experiments and calculations than the PW91 functional.     

从体系计算中讨论海森伯不确定关系

文章作者对量子力学与经典力学中的几个典型体系进行了计算,求出了粒子位置与动量的不确定量x2-x2和p2-p2.计算结果表明,不同状态下的不确定量之积是不一样的.谐振子和无限深势阱的实例计算还说明,与量子力学不确定关系相类似的关系在经典力学中也存在.它使人们对海森伯不确定关系有了新的认识,并对量子力学的波函数有了更深刻的了解.文章最后讨论了两个相关的实验现象.     

A theoretical study of thiophenic compounds adsorption on cation-exchanged Y zeolites

A density functional theory (DFT) method has been applied to study the adsorption of thiophenic compounds such as thiophene (TP), benzothiophene (BT), dibenzothiophene (DBT) on cation-exchanged Cu(I)Y, Ni(II)Y, Ce(III)Y zeolites. All of calculations were carried out by the generalized gradient approximation (GGA) with the BLYP exchange-correlation functional and DNP basis set. The calculated results indicate that the stable adsorption configuration of TP molecule adsorbed on the Cu(I)Y is the η5 adsorption mode, whereas for BT and DBT, the η1S adsorption mode was found for the both molecules. Only the η1S adsorption mode can be obtained for the three thiophenic compounds adsorbed on the Ni(II)Y. The η5 adsorption mode can be ascribed to the adsorption of thiophene molecules on the Ce(III)Y, but the competition of different adsorption modes could possibly occur during the adsorption process of BT and DBT on the Ce(III)Y. Moreover, the selectivity of TP adsorbed on the adsorbents is in the order of Cu(I)Y > Ce(III)Y > Ni(II)Y, while for BT and DBT, the order is Cu(I)Y > Ni(II)Y > Ce(III)Y.     

A theoretical study on various models for the domain boundaries in epitaxial GaN films

Various domain boundaries that are found in epitaxial Wurtzite GaN films were studied by molecular dynamics simulation. The Ewald summation algorithm and Keating potential model are adopted to calculate the long-range Coulomb interaction and the short-range bonding force in the semiconductor system, respectively. The research results show that the domain formation energies of (100) and (110) boundaries are significantly different. The latter ones have general quite higher formation energies than the formers. The like-atom (i.e. atoms of the same kind) bonding domain boundaries (LABDB) have higher formation energies than their counterparts of unlike-atom (i.e. atoms of different kinds) bonding domain boundaries (UABDB) in all GaN (100) and (110) interfaces. The UABDB structures are all stable while most of the LABDB are unstable. The advantage and the limitation of Keating potential model in Molecular Dynamics simulation for covalent crystal are discussed. Received: 7 April 1999 / Accepted: 1 November 1999 / Published online: 8 March 2000     

Adsorption of parent nitrosamine on the nanocrystaline H-zeolite: A theoretical study

Adsorption of parent nitrosamine (NA) on 5T and 10T cluster models of H-ZSM-5 catalyst has been theoretically investigated using quantum chemical B3LYP and MP2 methods. Three stable complexes (A-C) were found on the potential energy surface of interaction between NA and cluster models of H-ZSM-5. NA can interact not only with acidic site of zeolite via the lone electron pair on nitrogen and oxygen atoms (O(N)?H_ZO) but also with the oxygen atoms of the framework via the hydrogen atoms of NH₂ group (NH?O) as well. However, the Lewis acidity of zeolite framework is the dominating factor in the interaction between NA and zeolite. The calculated adsorption enthalpy of NA on 5T and 10T clusters of H-ZSM-5 catalyst at ONIOM(MP2/6-311++G(d,p):HF/6-31+G(d)) level ranges from −19.73 to −40.33 and −63.81 to −73.73 kJ/mol, respectively. Adsorption energy for A-C complexes increases in going from B3LYP method to MP2 one. The results of atoms in molecules (AIM) calculations showed that NH5?O interactions have electrostatic character, whereas O(N)?H_Z interactions have partially covalent nature. The results of natural bond orbital (NBO) analysis showed that charge transfer occurs from NA to H-zeolite cluster.     

Thermodynamics of Li-N-H system for hydrogen storage: A theoretical and experimental study

In the present work, electronic structure, chemical bonding and thermal stability of Li-N-H system for hydrogen storage were calculated by a first principle approach. On the basis of the thermal analysis of this system, pressure-composition-temperature (PCT) isotherm measurements of hydrogen desorption were performed and analyzed. The theoretical and experimental enthalpies of this system were calculated as −75.67 and −69.17 kJ/mol of H₂, which agree well with other corresponding findings of −73.6 and 66.1 kJ/mol of H₂, respectively. The theoretical and experimental values of desorption enthalpies in this study are reasonably agreeable with each other.     

Preliminary study on CAD-based method of characteristics for neutron transport calculation

Our new method makes use of a CAD-based automatic modeling tool, MCAM, for geometry modeling and ray tracing of particle transport in method of characteristics （MOC）. It was found that it could considerably enhance the capability of MOC to deal with more complicated models for neutron transport calculation. In our study, the diamond-difference scheme was applied to MOC to reduce the spatial discretization errors of the fiat flux approximation. Based on MCAM and MOC, a new 2D MOC code was developed and integrated into the SuperMC system, which is a Super Multi-function Computational system for neutronics and radiation simulation. The numerical results demonstrated the feasibility and effectiveness of the new method for neutron transport calculation in MOC.