Nucleophilic Addition to C,C-Double Bonds. Part VIII. The standard enthalpies of formation of anti9,10-10endo-hydroxytricyclo [4.2.1.12,5]deca-3,7-dien-9-one and 9-Oxatetracyclo [5.4.0.03,10.04,8]undec-5-en-2-one and kinetic data for the cyclization of the olefinic alcohol to the ether

In view of the significance of steric compression in the base-catalyzed intramolecular cyclization of polycyclic olefinic alcohols, the standard enthalpies of formation of anti^9,10-10 endo-hydroxytricyclo [4.2.1.1^2,5]deca-3,7-dien-9-one (1) and 9-oxatetracyclo [5.4.0.0^3,10.0^4,8]undec-5-en-2-one (2) as well as the kinetics of the ether formation 1 → 2 were determined.     

The vibrational force field of halogenated aromatic molecules: V. The CH stretching field in fluoroaromatics

It is shown that the average CH stretching frequencies in the fluoroaromatic series C₆H_6?nF_n depend on the fluorine substitution patterns, being given by v? = v?_B + _noX_o + _nmX_m + n_pX_p. Two variants on the general quadratic force field, which are taken to be transferable between members of the series, have been fitted to the experimental data. Each ortho fluorine substituent increases the diagonal CH stretching force constant by 1.0%. The dependence on meta and para substituents is not as obvious as with the average stretching frequency due to the rather large variance. A comparison with existing correlations between average stretching frequencies and bond length data indicates that an ortho fluorine atom leads to a CH bond shortening of 0.0017 A. Such information could prove of value in microwave structural investigations.     

Deviations from two-dimensionality in classical adsorbed films

The statistical mechanical theory of adsorption is presented as an expansion about the two-dimensional approximation. Two corrections to the latter are additive in the perturbation limit. One contribution, arising from the lateral variation of the substrate potential, has been previously evaluated. The second correction term is due to the particles' mutual interaction when their separation vector is not parallel to the surface. The latter is expressed in terms of the radial distribution function. Its contribution to the deviation from two-dimensionality is shown to be comparable to the first term for the case of a Lennard-Jones model.     

Calibration,validation, and verification including uncertainty of a physically motivated internal state variable plasticity and damage model

In this paper, we illustrate a formal calibration, validation, and verification process that includes uncertainty in an internal state variable plasticity-damage model that is implemented in a finite element code. The physically motivated continuum model characterizes damage evolution by incorporating material uncertainty due to microstructural spatial clustering. The uncertainty analysis is performed by introducing material variation through model validation and verification. The effect of variability in microstructural clustering and boundary conditions on the sensitivities and uncertainty of the plasticity-damage evolution for the 7075 aluminum alloy is characterized. The results show the potential of this methodology in the evaluation of material response uncertainty due to microstructure spatial clustering and its effect on damage evolution. For damage evolution, we have shown that the initial isotropic damage evolved into an anisotropic form as the deformation increased which is consistent with experimentally observed behavior for 7075 aluminum alloy in literature. Also, the sensitivities were found to be consistent with the physics of damage progression for this particular type of material. Through the sensitivity analysis, the initial defect size and number density of cracked particles are important at the beginning of deformation. As damage evolves, more voids are nucleated and grow and the sensitivity analysis illustrates this as well. Then, voids combine with each other and coalescence becomes the main driver, which is also confirmed by the sensitivity analysis. This work also shows that the microstructurally based damage evolution equations provide an accurate representation of the damage progression due to large intermetallic particles. Finally, we illustrate that the initial variation in the microstructure clustering can lead to about ±7.0%, ±8.1%, and ±9.75% variation in the elongation to failure strain for torsion, tensile, and compressive loading, respectively.     

A generic environment for modelling future launch operations—GEM-FLO: a success story in generic modelling

Several NASA programs have been established to study and improve the current launch capability to meet the need for more aggressive space exploration in the future. Numerous launch systems have been proposed by different government and commercial organizations with the potential goal of replacing the Space Shuttle. NASA must evaluate new designs and technologies with the objective of improving upon today's Shuttle cost, performance, and turnaround time, before the government or commercial organizations pursue the large undertaking of a new launch system. To address this issue, the Generic Simulation Environment for Modelling Future Launch Operations (GEM-FLO) was developed to accurately predict processing turnaround times and other effectiveness criteria and support making key business and program decisions. GEM-FLO utilizes a generic modelling paradigm to provide a single platform for modelling different designs, which helped significantly cut the cost of these studies. This paper documents a success story in generic simulation modelling.     

Synthesis,crystal structures and luminescent properties of phenylmercury(II) complexes with thiohydrazone ligands having weak Hg····π and Hg····Hg interactions

The Reaction of phenylmercury(II) acetate with salicylaldehyde morpholine N-thiohydrazone (H₂smth) and 2-hydroxyacetophenone morpholine N-thiohydrazone (H₂apmth) in dry ethanol under gentle refluxing condition form light yellow complexes [PhHg(Hsmth)] (1) and [PhHg(Hapmth)] (2) involving formation of Hg-S bond from the thiol form of the ligands after deprotonation of the SH proton. The structures of the complexes as determined by X-ray crystallography shows that the complex (1) has a distorted T-shaped geometry while the complex (2) adopts familiar linear coordination geometry. Complex (2) has two independent molecules comprising the asymmetric unit. Both the complexes form two-dimensional supramolecular assemblies due to a combination of weak intermolecular Hg····π and Hg····Hg interactions. The Hg····π and Hg····Hg distances are 3.937 and 4.0216(10) Å, respectively, possibly indicating weak mercuriophilic interactions. The luminescent properties of the complexes in solution and in the solid state at room temperature are also described.     

Polymorphism of the borophosphate anion in K(Fe,Al)[BP<Subscript>2</Subscript>O<Subscript>8</Subscript>(OH)] and Rb(Al,Fe)[BP<Subscript>2</Subscript>O<Subscript>8</Subscript>(OH)] crystal structures

The crystal structure of two borophosphates, Rb(Al,Fe)[BP₂O₈(OH)] (a = 9.381(6), b = 8.398(5), c = 9.579(6) Å, β = 102.605(10)°, sp. gr. P2₁/c) and K(Fe,Al)[BP₂O₈(OH)] (a = 5.139(2), b = 8.065(4), c = 8.290(4)Å, α = 86.841(8)°, β = 80.346(8)°, γ = 86.622(8)°, sp. gr. P \(\bar 1\)), obtained by hydrothermal synthesis in the AlCl₃: FeCl₃: K₃PO₄(Rb₃PO₄): B₂O₃: H₂O system has been established using X-ray diffraction (Bruker Smart diffractometer, T = 100 K). Hydrogen atoms are located and their coordinates and thermal parameters are refined. It is shown that the polymorphism of the [BP₂O₈(OH)]^4? borophosphate anion has a morphotropic nature and is related to the substitutions both in the cationic part of the structure and in the octahedral position of the anionic mixed framework. The synthesis of new isotypic triclinic compounds under hydrothermal conditions is predicted.