Direct estimation of an element of order matrix from H-1 NMR spectra of strongly dipolar coupled spins

NMR spectra of molecules oriented in thermotropic liquid crystalline media provide information on the molecular structure and order. The spins are generally strongly dipolar coupled and the spectral analyse require the tedious and time consuming numerical iterative calculations. The present study demonstrates the application of multiple quantum spin state selective detection of single quantum transitions for mimicking the homonuclear decoupling and the direct estimation of an element of ordering matrix. This information is utilized to estimate the nearly accurate starting dipolar couplings for iterative calculations. The studies on the spectra of strongly dipolar coupled five and six interacting spin systems are reported.

On the origin of the inflectional instability of a laminar separation bubble

This is an experimental and theoretical Study of a laminar separation bubble and the associated linear stability mechanisms. Experiments were performed over a flat plate kept in a wind tunnel, with an imposed pressure gradient typical of an aerofoil that would involve a laminar separation bubble. The separation bubble was characterized by measurement of surface-pressure distribution and streamwise velocity using hot-wire anemometry. Single component hot-wire anemometry was also used for a detailed study of the transition dynamics. It was foundthat the so-called dead-air region in the front portion of the bubble corresponded to a region of small disturbance amplitudes, with the amplitude reaching a maximum value close to the reattachment point. An exponential growth rate of the disturbance was seen in the region upstream of the mean maximum height of the bubble, and this was indicative of a linear instability mechanism at work. An infinitesimal disturbance was impulsively introduced into the boundary layer upstream of separation location, and the wave packet was tracked (in an ensemble-averaged sense) while it was getting advected downstream. The disturbance was found to be convective in nature. Linear stability analyses (both the Orr-Sommerfeld and Rayleigh calculations) were performed for mean velocity profiles, starting from an attached adverse-pressure-gradient boundary layer all the way up to the front portion of the separation-bubble region (i.e. up to the end of the dead-air region in which linear evolution of the disturbance could be expected). The conclusion from the present work is that the primary instability mechanism in a separation bubble is inflectional in nature, and its origin can be traced back to upstream of the separation location. In other words, the inviscid inflectional instability of the separated shear layer should be logically seen as an extension of the instability of the upstream attached adverse-pressure-gradient boundary layer. This modifies the traditional view that pegs the origin of the instability in a separation bubble to the detached shear layer Outside the bubble, with its associated Kelvin-Helmholtz mechanism. We contendthat only when the separated shear layer has moved considerably away from the wall (and this happens near the maximum-height location of the mean bubble), a description by the Kelvin-Helmholtz instability paradigm, with its associated scaling principles, Could become relevant. We also propose a new scaling for the most amplified frequency for a wall-bounded shear layer in terms of the inflection-point height and the vorticity thickness and show it to be universal.

A molecular dynamics investigation of the structure of PbO---PbF2 glasses*1

The structure of PbO---PbF2 glasses has been studied using molecular dynamics (MD). The existence of [OPb4] structural units is observed over the entire glass-forming range, in conformity with a model proposed earlier based on various structural investigations of this system. Various other features of the structural model are also supported by the MD calculations.

A linear root water uptake model

A model of root water extraction is proposed, in which a linear variation of extraction rate with depth is assumed. Five crops are chosen for simulation studies of the model, and soil moisture depletion under optimal conditions from different layers for each crop is calculated. Similar calculations are also made using the constant extraction rate model. Rooting depth is assumed to vary linearly with potential evapotranspiration for each crop during the vegetative phase. The calculated depletion patterns are compared with measured mean depletion patterns for each crop. It is shown that the constant extraction rate model results in large errors in the prediction of soil moisture depletion, while the proposed linear extraction rate model gives satisfactory results. Hypothetical depletion patterns predicted by the model in combination with a moisture tension-dependent sink term developed elsewhere are indicated.

Computer simulation of polytypes

Polytypes have been simulated, treating them as analogues of a one-dimensional spin-half Ising chain with competing short-range and infinite-range interactions. Short-range interactions are treated as random variables to approximate conditions of growth from melt as well as from vapour. Besides ordered polytypes up to 12R, short stretches of long-period polytypes (up to 33R) have been observed. Such long-period sequences could be of significance in the context of Frank's theory of polytypism. The form of short-range interactions employed in the study has been justified by carrying out model potential calculations.

Valence bond analysis of the Kondo chain Hamiltonian

Accurate extrapolations for the ground state energy per site of the one - dimensional Kondo chain system is obtained from exact finite system calculations carried out employing a valence bond scheme. An analysis of the ground state wave function indicates that the localized spin is quenched for all nonzero values of the Kondo exchange constant in one dimension.

Chlorinated Hypoelectronic Dimetallaborane Clusters: Synthesis, Characterization, and Electronic Structures of (eta(5)-C5Me5W)(2)B5HnClm (n=7, m=2 and n=8, m=1)

Pyrolysis of (eta(5)-C5Me5WH3)B4H8, 1, in the presence of excess BHCl2 center dot SMe2 in toluene at 100 degrees C led to the isolation of (eta(5)-C5Me5W)(2)B5H9, 2, and B-Cl inserted (eta(5)-C5Me5W)(2)B5H8Cl, 3, and (eta(5)-C5Me5W)(2)B5H7Cl2, (four isomers). All the Chlorinated tungstaboranes were isolated as red and air and moisture sensitive solids. These new compounds have been characterized in solution by H-1, B-11, C-13 NMR, and the structural types were unequivocally established by crystallographic analysis of compounds 3, 4, and 7. Density functional theory (DFT) calculations were carded out on the model molecules of 3-7 to elucidate the actual electronic structures of these chlorinated species. On grounds of DFT calculations we demonstrated the role of transition metals, bridging hydrogens, and the effect of electrophilic substitution of hydrogens at B-H vertices of metallaborane structures.

Sol → gel transition with rings in a finite polycondensing system in solution

We report a theoretical formulation for the mean cluster size distribution in a finite polycondensing system. Expressions for the mean number of n-mers with j bonds ( nj) are developed. Numerical calculations show that while the non-cyclic molecules make the dominant contribution to the small clusters, the large clusters are dominated by cyclic structures. The number of particles in ringless chains, n n,n-1, decays monotonically with n at all extents of reaction, but n n becomes bimodal near the gel point. We also find that the solvent plays an important role in the cluster size distribution.

Infrared spectra of 1.3-dithiole-2-thione and its selenium analogues ând frequency assignment and molecular force constants

Infrared spectra of 1,3-dithiole-2-thione (DTT) and its four selenium analogues have been studied in the region 4000 to 20 cm�1. Assignment of all the fundamental frequencies was made by noting the band shifts on progressive selenation. Normal coordinate analysis procedures have been applied for both in-plane and out-of-plane vibrations to help the assignments. The Urey�Bradley force function supplemented with valence force constants for the out-of-plane vibrations was employed for coordinate calculations. A correlation of the infrared assignments of DTT with its different selenium analogues is accomplished. Further, the infrared assignments are compared with those of trithiocarbonate ion and its selenium analogues and other structurally related heterocyclic molecules.

Economic case study of ABCD cane management practices in the Burdekin River Irrigation Area (BRIA) region

A case study was undertaken to determine the economic impact of a change in management class as detailed in the A, B, C and D management class framework. This document focuses on the implications of changing from D to C, C to B and B to A class management in the Burdekin River irrigation area (BRIA) and if the change is worthwhile from an economic perspective. This report provides a guide to the economic impact that may be expected when undertaking a particular change in farming practices and will ultimately lead to more informed decisions being made by key industry stakeholders. It is recognised that these management classes have certain limitations and in many cases the grouping of practices may not be reflective of the real situation. The economic case study is based on the A, B, C and D management class framework for water quality improvement developed in 2007/2008 for the Burdekin natural resource management region. The framework for the Burdekin is currently being updated to clarify some issues and incorporate new knowledge since the earlier version of the framework. However, this updated version is not yet complete and so the Paddock to Reef project has used the most current available version of the framework for the modelling and economics. As part of the project specification, sugarcane crop production data for the BRIA was provided by the APSIM model. The information obtained from the APSIM crop modelling programme included sugarcane yields and legume grain yield (legume grain yield only applies to A class management practice). Because of the complexity involved in the economic calculations, a combination of the FEAT, PiRisk and a custom made spreadsheet was used for the economic analysis. Figures calculated in the FEAT program were transferred to the custom made spreadsheet to develop a discounted cash flow analysis. The marginal cash flow differences for each farming system were simulated over a 5-year and 10-year planning horizon to determine the net present value of changing across different management practices. PiRisk was used to test uncertain parameters in the economic analysis and the potential risk associated with a change in value.

Economic case study of ABCD cane management practices in the Burdekin Delta region.

A case study was undertaken to determine the economic impact of a change in management class as detailed in the A, B, C and D management class framework. This document focuses on the implications of changing from D to C, C to B and B to A class management in the Burdekin Delta region and if the change is worthwhile from an economic perspective. This report provides a guide to the economic impact that may be expected when undertaking a particular change in farming practices and will ultimately lead to more informed decisions being made by key industry stakeholders. It is recognised that these management classes have certain limitations and in many cases the grouping of practices may not be reflective of the real situation. The economic case study is based on the A, B, C and D management class framework for water quality improvement developed in 2007/2008 for the Burdekin natural resource management region. The framework for the Burdekin is currently being updated to clarify some issues and incorporate new knowledge since the earlier version of the framework. However, this updated version is not yet complete and so the Paddock to Reef project has used the most current available version of the framework for the modelling and economics. As part of the project specification, sugarcane crop production data for the Burdekin Delta region was provided by the APSIM model. The information obtained from the APSIM crop modelling programme included sugarcane yields and legume grain yield (legume grain yield only applies to A class management practice). Because of the complexity involved in the economic calculations, a combination of the FEAT, PiRisk and a custom made spreadsheet was used for the economic analysis. Figures calculated in the FEAT program were transferred to the custom made spreadsheet to develop a discounted cash flow analysis. The marginal cash flow differences for each farming system were simulated over a 5-year and 10-year planning horizon to determine the Net Present Value of changing across different management practices. PiRisk was used to test uncertain parameters in the economic analysis and the potential risk associated with a change in value.

Economic case study of ABCD cane management practices in the Tully region

A case study was undertaken to determine the economic impact of a change in management class as detailed in the A, B, C and D management class framework. This document focuses on the implications of changing from D to C, C to B and B to A class management in the Tully region and if the change is worthwhile from an economic perspective. This report provides a guide to the economic impact that may be expected when undertaking a particular change in farming practices and will ultimately lead to more informed decisions being made by key industry stakeholders. It is recognised that these management classes have certain limitations and in many cases the grouping of practices may not be reflective of the real situation. The economic case study is based on the A, B, C and D management class framework for water quality improvement developed in 2007/2008 by the wet tropics natural resource management region. The framework for wet tropics is currently being updated to clarify some issues and incorporate new knowledge since the earlier version of the framework. However, this updated version is not yet complete and so the Paddock to Reef project has used the most current available version of the framework for the modelling and economics. As part of the project specification, sugarcane crop production data for the Tully region was provided by the APSIM model. Because of the complexity involved in the economic calculations, a combination of the FEAT, PiRisk and a custom made spreadsheet was used for the economic analysis. Figures calculated in the FEAT program were transferred to the custom made spreadsheet to develop a discounted cash flow analysis. The marginal cash flow differences for each farming system were simulated over a 5-year and 10-year planning horizon to determine the Net Present Value of changing across different management practices. PiRisk was used to test uncertain parameters in the economic analysis and the potential risk associated with a change in value.

Closo versus Hypercloso Metallaboranes: A DFT Study

The structures and electronic relationship of 9-, 10-, 11-, and 12-vertex closo and hypercloso (isocloso) etallaboranes are explored using OFT calculations. The role of the transition metal in stabilizing the hypercloso borane structures is explained using the concept of orbital compatibility. The hypercloso structures, C6H6MBn-1Hn-1 (n = 9-12; M = Fe, Ru, and Os) are taken as model complexes. Calculations on metal free polyhedral borane BnHn suggest that n vertex hypercloso structures need only n skeleton electron pairs (SEPs), but the structure will have one or more six-degree vertices, whereas the corresponding closo structures with n + 1 SEPs have only four- and five-degree vertices. This high-degree vertex of hypercloso structures can be effectively occupied by transition metal fragments with their highly diffused orbitals. Calculations further show that a heavy transition metal with more diffused orbitals prefers over a light transition metal to form hypercloso geometry, This is in accordance with the fact that there are more experimentally characterized hypercloso structures with the heavy transition metals. The size of the exohedral ligands attached to the metal atom also plays a role in deciding the stability of the hypercloso structure. The interaction between the borane and the metal fragments in the hypercloso geometry is analyzed using the fragment molecular orbital approach. The interconversion of the closo and hypercloso structures by the addition and removal of the electrons is also discussed in terms of the correlation diagrams.

X-Pro peptides. A theoretical study of the hydrogen bonded conformations of (alpha-aminoisobutyryl-L -prolyl)n sequences

Intramolecularly hydrogen bonded conformations of (Aib-Pro)n sequences have been analysed theoretically. Both 4-1 (C10 and 3-1 (C7 hydrogen bonded regular structures are shown to be stereochemically feasible. Conformational energies for the helical structures have been estimated using classical potential energy methods. Both C10 and C7 conformations have very similar energies. Pyrrolidine ring puckering has a pronounced effect on the energies, and only Cv-endo puckered Pro residues can be accommodated. The theoretical calculations using spectroscopic data suggest that the recently proposed novel 310 helical conformation for benzyloxycarbonyl(Aib-Pro)4-methyl ester is in solution, is indeed energetically and stereochemically favourable.

Heats of reaction between aniline and formaldehyde by solution calorimetry: Reaction in neutral medium

The enthalpies of reaction between aniline and HCHO at various molar proportions under neutral conditions were determined by solution calorimetry. These measurements are new in the field of aniline and HCHO condensation polymers. The specific heats of the products formed were determined by differential scanning calorimetry and were used in the enthalpy calculations. Plots of enthalpy of reaction calculated with respect to aniline and HCHO vs. different A/F molar ratios were made. From the enthalpy data it appears that the reactions between different A/F molar ratios yield different products.