An improved potential surface for formaldehyde

A potential energy surface for the ground X? ¹A₁ state of H₂CO has been derived, which reproduces the position of a recently calculated H₂ + CO transition state. The variational method for the determination of frequencies of potential energy surfaces has been extended to tetra-atomics, thus enabling the surface to be refined.     

An SCF potential energy surface for lithium cyanide

Ab initio SCF calculations are performed for LiCN using a large polarised GTO basis. An analytic fit to the two-dimensional surface (the CN bond length is frozen at 2.186 a₀) is presented.     

An improved method for high-performance liquid chromatography of gossypol

Earlier liquid-chromatographic methods for the determination of gossypol, based on highly acidic methanolic solvents, provide broad tailing peaks. The use of acetonitrile with aqueous phosphoric acid/tri-n-butylammonium phosphate at pH 3.5 and a high-resolution radial-compression column gave greatly improved performance and excellent peak shape.     

An improved collision efficiency model for particle aggregation

A generalized geometric model is presented which describes the collision efficiency factor of aggregation (the probability of a binary particle or aggregate collision resulting in adhesion) for systems comprised of two oppositely charged species. Application of the general model to specific systems requires calculation of the area of each species available for collision with a second species. This is in contrast to previous models developed for polymer-particle flocculation that are based on the fractional surface coverage of adsorbed polymer. The difference between these approaches is suggested as an explanation for previously observed discrepancies between theory and observation. In the current work the specific case of oppositely charged nondeformable spherical particles (heteroaggregation) is quantitatively addressed. The optimum concentration of oppositely charged particles for rapid aggregation (maximum collision efficiency) as a function of relative particle size is calculated and an excellent correlation is found with data taken from literature.     

An improved model for crystalline orientation of spherulitic polymers

A model is proposed to account for the orientation of crystals in spherulites upon deforming a polymer. The model assumes affine deformation of the spherulite accompanied by three processes of crystal reorientation within the spherulite. These are tilting of molecular chains with respect to the plane of the lamellae, characterized by a parameter K, twisting of the lamallae about the spherulite radii described by η, and rotation of the b crystal axis about the c axis characterized by a third parameter, P. Values of these parameters are fitted to measured orientation functions and compared with experimental measurements of the azimuthal variation of the intensities of the 110 and 200 crystal reflections from low-density polyethylene. Good agreement is found between the experimental and theoretically predicted intensity variation. Time-dependent experiments under relaxational and vibrational conditions are also treated by the theory.     

An improved meniscus surface model for contacting rough surfaces

Based on the Extended-Maugis-Dugdale (EMD) elastic theory, a single asperity capillary meniscus model considering asperity deformation due to both contact and adhesive forces was developed. Specifically included in the single asperity meniscus model was the solid surface interaction inside the contact area. Subsequently, the single asperity model was coupled with a statistical roughness surface model to develop an improved meniscus surface model applicable to a wide-range of humidity levels and adhesion parameter values. Simulations were performed using typical surfaces found in microelectromechanical systems (MEMS) and magnetic storage hard disk drives to examine the effects of surface roughness and relative humidity. It was found that smoother surfaces give rise to higher adhesive and pull-off forces, and at higher relative humidity levels, the capillary force governs the adhesive behavior. As the humidity decreases, the solid surface interaction increases and needs to be included in the total meniscus adhesion. By integrating the adhesive force-displacement curves, the adhesion energy per unit area was calculated for MEMS surfaces and favorably compared with reported experimental data.     

An equation-of-state-based viscosity model for non-ideal liquid mixtures

A viscosity model based on the Eyring’s theory and a cubic equation of state (Peng–Robinson–Stryjek–Vera) has been applied to the correlation and prediction of experimental liquid viscosities of binary mixtures containing polar fluids within a wide range of temperature, pressure and composition (encompassing low-pressure and compressed liquid conditions). Highly non-idealities of the binary mixtures considered in this study were conveniently handled via the application of the Wong–Sandler approach for the mixing rules used in the cubic equation of state. The results obtained were highly satisfactory for various non-ideal binary mixtures over the whole composition range at a low pressure. The predictive capabilities of the present approach were also verified in the representation of liquid viscosities at elevated pressures preserving the same model parameters previously obtained at low pressure.     

First-order model potential for optical dipole transitions: Application to the lithium isoelectronic sequence

We have constructed two first-order model potentials which were designed to yield dipole transition moments, and have applied them to the lithium isoelectronic sequence. The models contain two or three adjustable parameters, chosen so as to reproduce selected transition moment data on a single ion of the sequence. With negligible computational effort, they both yield other transition moments of high accuracy.     

An improved Space-Charge model for flow through charged microporous membranes

The Space-Charge model is modified to better analyze the steady-state electrohydrodynamic behavior of aqueous monovalent electrolytes in charged microporous membranes. The effects of changes in solvent dielectric constant near the wall, ion hydration effects, finite ion sizes, and charge regulating surface effects, are incorporated into the governing electrohydrodynamic equations (i.e., Navier-Stokes (NSE), Nernst-Planck (NPE), and Poisson-Boltzmann (PBE) equations). Their effect on streaming potential, pore conductivity, excess conductivity, and maximum energy conversion efficiency for electro-osmosis is illustrated. It is shown that the dielectric saturation and ion hydration effects cause significant changes in the electric potential field and ion concentration inside the capillary tubes. Quantitative comparisons of model results with measured electrokinetic data reveal better agreement when compared with the existing model.     

An accurate and simple quantum model for liquid water

The path-integral molecular dynamics and centroid molecular dynamics methods have been applied to investigate the behavior of liquid water at ambient conditions starting from a recently developed simple point charge/flexible (SPC/Fw) model. Several quantum structural, thermodynamic, and dynamical properties have been computed and compared to the corresponding classical values, as well as to the available experimental data. The path-integral molecular dynamics simulations show that the inclusion of quantum effects results in a less structured liquid with a reduced amount of hydrogen bonding in comparison to its classical analog. The nuclear quantization also leads to a smaller dielectric constant and a larger diffusion coefficient relative to the corresponding classical values. Collective and single molecule time correlation functions show a faster decay than their classical counterparts. Good agreement with the experimental measurements in the low-frequency region is obtained for the quantum infrared spectrum, which also shows a higher intensity and a redshift relative to its classical analog. A modification of the original parametrization of the SPC/Fw model is suggested and tested in order to construct an accurate quantum model, called q-SPC/Fw, for liquid water. The quantum results for several thermodynamic and dynamical properties computed with the new model are shown to be in a significantly better agreement with the experimental data. Finally, a force-matching approach was applied to the q-SPC/Fw model to derive an effective quantum force field for liquid water in which the effects due to the nuclear quantization are explicitly distinguished from those due to the underlying molecular interactions. Thermodynamic and dynamical properties computed using standard classical simulations with this effective quantum potential are found in excellent agreement with those obtained from significantly more computationally demanding full centroid molecular dynamics simulations. The present results suggest that the inclusion of nuclear quantum effects into an empirical model for water enhances the ability of such model to faithfully represent experimental data, presumably through an increased ability of the model itself to capture realistic physical effects.     

An improved potential energy surface for the F+H2 reaction

A new ground state potential energy surface has been developed for the F+H₂ reaction. Using the UCCSD(T) method, ab initio calculations were performed for 786 geometries located mainly in the exit channel of the reaction. The new data was used to correct exit channel errors that have become apparent in the potential energy surface of Stark and Werner [J. Chem. Phys. 104 (1996) 6515]. While the entrance channel and saddlepoint properties of the Stark–Werner surface are unchanged on the new potential, the exit channel behavior is more satisfactory. The exothermicity on the new surface is much closer to the experimental value. The new surface also greatly diminishes the exit channel van der Waals well that was too pronounced on the Stark–Werner surface. Several preliminary dynamical scattering calculations were carried out using the new surface for total angular momentum equal to zero for F+H₂ and F+HD. It is found that gross features of the reaction dynamics are quite similar to those predicted by the Stark–Werner surface, in particular the reactive resonance for F+HD and F+H₂ survive. However, the most of the exit channel van der Waals resonances disappear on the new surface. It is predicted that the differential cross-sections at low collision energy for the F+H₂ reaction may be drastically modified from the predictions based on the Stark–Werner surface.     

Temperature and density dependence of the structure of liquid lithium from an improved pseudopotential theory

Leribaux, H.R., and Lemarchand, J.L., 1978. Temperature and density dependence of the structure of liquid lithium from an improved pseudopotential theory. Fluid Phase Equilibria, 2: 79–90.The structure of liquid lithium and alloys has recently been measured more accurately near their melting point. We present for liquid lithium a modification of a previous pseudopotential for liquid metals, obtained by including explicitly the Xα exchange energy in the electron pseudopotential. The structure factor S(q), obtained from this model potential via the effective pair potential, and calculated by our solution of the Percus—Yevick equation, is found to have the right oscillations compared with the experimental structure factor, the first peak also having the right magnitude. A Percus—Yevick hard-sphere structure factor is also obtained via thermodynamic perturbation and is found to be surprisingly good even for lithium, except for the high-q oscillations. We present computed structures and radial distributions for several higher temperatures involved typically in the liquid lithium alloys, up to the highest temperatures at which saturated density is measured. Our model potential predicts also the correct cohesive energy for liquid lithium and liquid lithium—magnesium.     

Mesoporous cobalt oxide for largely improved lithium storage properties

We report the microstructure,application for lithium-ion batteries of mesoporous Co3O4 prepared by modified KIT-6 template method.The sample was characterized by XRD,TEM,HRTEM and nitrogen adsorption.Their electrochemical behaviors as electrode reactants for lithium ion batteries were evaluated by cyclic voltammograms and static charge-discharge.A direct comparison of electrochemical behaviors between mesoporous nanostructure and bulk reflects interesting "nanostructure effect",which is reasonably discussed in terms of how the 3D nanostructures of Co3O4 materials function in tuning their electrochemistry.The results demonstrate that further improvement of electrochemical performance in transition metal-oxide-based anode materials can be realized via the design of multiporous nanostructured materials.     

An improved liquid chromatographic method for the analysis of tylosin and its impurities

A selective reversed-phase (RP) liquid chromatographic (LC) method coupled with UV for the determination of tylosin and its related substances is described. The gradient method uses a Capcell pak C18 ACR column (25 cm×4.6 mm id, 5 μm) maintained at a temperature of 60°C. The mobile phases consist of acetonitrile, phosphate buffer pH 5.5 and water: (A; 27.5:10:62.5 v/v/v) and (B; 50:10:40 v/v/v). The flow rate is 1.0 mL/min and UV detection is performed at 280 nm. It allows the separation of all known and 22 other unknown related substances (≥0.02%) from the main compound and from one another. The method shows good precision, sensitivity, linearity (between 0.2 μg/mL and 1.25 mg/mL) and robustness. The limit of quantification is 0.2 μg/mL, corresponding to 0.020%. Seven bulk tylosin samples containing a large number of impurities were examined using this method.     

An improved interface for liquid chromatography/electron-capture detector coupling. Part II

Summary An improved interface for the coupling of a liquid chromatograph (LC) and an electron-capture detector (ECD) allows the use of the LC-ECD combination for the determination of various types of chlorinated aromatic compounds. The addition of up to 6% of dioxan to the hexane used as mobile phase can be tolerated without serious deterioration of detector performance. Derivatization of polar compounds such as anilines, phenylurea herbicides, chlorophenols and hydroxylated polychlorobiphenyls with fluorine-and non-fluorine-containing acid anhydrides is a useful tool to extend the application range of LC-ECD. As an example, the analysis of a spiked soil sample is discussed.Presented at the 14th International Symposium on Chromatography London, September, 1982     

An improved heat transfer model for building phase change material wallboard

Journal of Thermal Analysis and Calorimetry - For improving the accuracy of the effective heat capacity model and increasing the computing speed of the enthalpy model, an improved numerical model...     

An improved Helmholtz energy model for air and the related systems

In this work a Helmholtz energy model is applied to the prediction of thermodynamic properties of air, the related binary mixtures and the intervening pure components. The Helmholtz energy of the mixture is represented as two contributions: one from a proven accurate extended corresponding states model and the other is a correction term. The corresponding states model relies on pure-component shape factors relative to nitrogen and extension to mixtures with the van der Waals one-fluid mixture model with ordinary combining rules. The correction term is temperature-, density- and composition-dependent with the use of a theoretically consistent local composition model with a coordination number model derived from lattice gas theory. For air the obtained average absolute deviations in densities were 0.090 per cent, 0.15 per cent in speeds of sound, 0.28 per cent in bubble-point pressures and 0.30 per cent for dew-point pressures. For the three associated binary mixtures, the absolute average deviations in densities were within 0.14 per cent and 0.63 per cent for bubble-point pressures. For oxygen and argon, the absolute average deviations were within 0.07 per cent in densities, 0.45 per cent in VLE properties and 0.012 per cent in speeds of sound.