The electronic origin of unusually large nJFN coupling constants in some fluoroximes

SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through‐space transmission of J_FN coupling constants for the fluoroximes studied in this work. Because of the well‐known behavior of FC term, a new rationalization for the experimental ^TSJ_FN SSCC is presented. It is mainly based on the overlap matrix (S_ij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (D_ij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non‐bonding electron pairs involved in D_ij. In using this approach, a linear correlation between ^TSJ_FN versus D_ij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so‐called through‐space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through‐space coupling, it should better be dubbed as ‘through overlapping orbital coupling’. Copyright © 2013 John Wiley & Sons, Ltd.     

Stereochemical dependence of 3JCH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives

Theoretical and experimental studies on (3)J(C2H6eq) NMR spin-spin coupling constants in both the 2-X-4-t-butyl-cyclohexanone (X = H, CH(3), F, Cl, and Br) and in their alcohol derivatives series are reported. Results thus found are rationalized in terms of the transmission of the Fermi contact contribution to such couplings. To this end, dependencies of (3)J(C2H6eq) couplings versus the C(2)-C(1)-C(6) angle are compared in both series for equatorial and axial X orientations. The main trend is described in terms of the rear lobes interaction. Besides, for X = halogen atom in equatorial orientation a rather strong interaction between oxygen and halogen lone pairs is observed, and its influence on (3)J(C2H6eq) couplings is discussed and rationalized in terms of different Fermi contact transmission pathways.     

Heat flux between parallel plates through a binary gaseous mixture over the whole range of the Knudsen number

The heat flux problem for a binary gaseous mixture confined between two parallel plates with different temperatures is studied on the basis of the McCormack kinetic model equation, which was solved by the discrete velocity method. The calculations were carried out for three mixtures of noble gases: neon–argon, helium–argon and helium–xenon. The heat flux and distributions of temperature, density and concentration were calculated for several values of rarefaction in the range from 0.01 to 40 and for three values of the concentration: 0.1,0.5$0.1,0.5$ and 0.9$0.9$. The numerical data together with an analytical solution based on the temperature jump boundary condition cover the whole range of the gas rarefaction beginning from the free-molecular regime to the hydrodynamic one. It was shown that the heat flux significantly depends on the intermolecular interaction law.     

Effect of electronic interactions on NMR 1J(CF) and 2J(CF) couplings in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives

In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on (1)J(CF) and (2)J(CF) NMR spin-spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin-orbit (PSO), and diamagnetic spin-orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of (2)J(CF) SSCC in cis-4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds.     

Onsager-Casimir Reciprocal Relations Based on the Boltzmann Equation and Gas-Surface Interaction. Gaseous Mixtures

The approach to the Onsager-Casimir reciprocity relations based on the linearized Boltzmann equation and gas-surface interaction law regarding kinetic coefficients which are neither odd nor even with respect to time reversal is applied to gaseous mixtures. As an example, the slip velocity problem is considered. It is shown that using the reciprocal relations the viscous, thermal and diffuse slip coefficients can be calculated simultaneously solving a unique kinetic coefficient. PACS: 05.70.Ln     

Hybrid films based on hydroxylated castor oil and titanium(IV) isopropoxide

Novel organic–inorganic hybrid films were synthesized by the reaction of hydroxylated castor oil (HCO) with titanium(IV) isopropoxide (TIP) in which the mass proportions of organic to inorganic precursor varied from 95:5 to 85:15. Films were pre-cured at room temperature under an inert atmosphere and subsequently submitted to thermal curing. The macro- and microscopic properties of the films, including adhesion, hardness, microstructure (SEM and AFM) and thermal properties, were determined as a function of the proportion of HCO to TIP. Morphologic studies showed that the hybrid films were microscopically homogeneous. The hardness and tensile strength of the films increased, with increased concentration of inorganic precursor. All of the films exhibited good adhesion to an aluminum surface.     

19F DOSY NMR analysis for spin systems with nJFF couplings

NMR is a powerful method for identification and quantification of drug components and contaminations. These problems present themselves as mixtures, and here, one of the most powerful tools is DOSY. DOSY works best when there is no spectral overlap between components, so drugs containing fluorine substituents are well‐suited for DOSY analysis as ¹⁹F spectra are typically very sparse. Here, we demonstrate the use of a modified ¹⁹F DOSY experiment (on the basis of the Oneshot sequences) for various fluorinated benzenes. For compounds with significant ⁿJ_FF coupling constants, as is common, the undesirable J‐modulation can be efficiently suppressed using the Oneshot45 pulse sequence. This investigation highlights ¹⁹F DOSY as a valuable and robust method for analysis of molecular systems containing fluorine atoms even where there are large fluorine–fluorine couplings. Copyright © 2014 John Wiley & Sons, Ltd.     

Plane Couette flow of binary gaseous mixture in the whole range of the Knudsen number

The Couette flow of binary gaseous mixtures is studied on the basis of the McCormack model of the Boltzmann equation, which was solved numerically by the discrete velocity method. The calculations were carried out for three mixtures of noble gases: neon–argon, helium–argon, and helium–xenon. The stress tensor and bulk velocity of both species were calculated for several values of the gas rarefaction in the range from 0.01 to 40 for three values of the molar concentrations: 0.1,0.5 and 0.9. The numerical solution together with an analytical solution based on the slip boundary condition cover the whole range of the gas rarefaction. It was showed that the Couette flow is weakly affected by the intermolecular interaction law.     

Discrete velocity modelling of gaseous mixture flows in MEMS

The need of developing advanced micro-electro-mechanical systems (MEMS) has motivated the study of fluid-thermal flows in devices with micro-scale geometries. In many MEMS applications the Knudsen number varies in the range from 10⁻² to 10². This flow regime can be treated neither as a continuum nor as a free molecular flow. In order to describe these flows it is necessary to implement the Boltzmann equation (BE) or simplified kinetic model equations.The aim of the present work is to propose an efficient methodology for solving internal flows of binary gaseous mixtures in rectangular channels due to small pressure gradients over the whole range of the Knudsen number. The complicated collision integral term of the BE is substituted by the kinetic model proposed by McCormack for gaseous mixtures. The discrete velocity method is implemented to solve in an iterative manner the system of the kinetic equations. Even more the required computational effort is significantly reduced, by accelerating the convergence rate of the iteration scheme. This is achieved by formulating a set of moment equations, which are solved jointly with the transport equations.The velocity profiles and the flow rates of three different binary mixtures (He–Ar, Ne–Ar and He–Xe) in 2D micro-channels of various height to width ratios are calculated. The whole formulation becomes very efficient and can be implemented as an alternative methodology to the classical method of solving the Navier–Stokes equations with slip boundary conditions, which in any case is restricted by the hydrodynamic regime.