The extent of molecular orientation at liquid/vapor interface of pyridine and its alkyl derivatives by molecular dynamics simulation

In this paper, molecular dynamics simulation was performed to investigate the liquid∕vapor interfacial structure of neat polar liquids. Large-scale ensembles of liquid pyridine and its alkyl derivatives, 4-methylpyridine and 4-ethylpyridine, were simulated by classical molecular dynamics at 298 K. For the liquid system of low polarity, the surface density profile of the atoms meet exactly at the middle of interfacial region, and atoms of hydrophobic nature can be hardly discriminated from hydrophilic ones in either vapor or liquid sides. For a liquid system of high polarity, the density profile of atoms with different nature is highly discriminated all over the interfacial region, and as the polarity increases, a dense region of atomic density is clearly developed in the subsurface region. The recognized bivariate method was also used to study the molecular orientational distribution quantitatively. Orientational analysis of the three liquid systems indicates that the pyridine ring plane in the outmost surface tends to be vertical. Its tendency in the innermost interfacial region is parallel. The orientational states available to 4-ethylpyridine and pyridine are discriminated by predicting the possibility of a bisector-wise tumbling for the ring plane in pyridine and a side-wise tumbling in 4-ethylpyridine. The orientational distribution maps explain the trend of experimental surface tension and surface entropy. As the dipole moment of these liquids increases with the alkyl chain length, the surface structural profile changes from a regular definite one to a surface of complex atomic structure involving a dense phase near the interface. The development of dense region in alkyl derivatives is the result of segregation of molecules due to the alkyl group, which is captured and discriminated by molecular dynamics simulation even when the length of a short alkyl chain is increased by one carbon atom.     

Faltings’ local–global principle for finiteness dimension of cofinite modules

Archiv der Mathematik - Let R denote a commutative Noetherian ring, $$\mathfrak {a}$$ an ideal of R, and M an $$\mathfrak {a}$$ -cofinite R-module. The purpose of this article is to show that for a...     

Variational transition state theory with multidimensional tunnelling and kinetic isotope effects in the reactions of C2H6, C2H5D and C2D6 with .CCl3 to produce CHCl3 and CDCl3

ABSTRACT

Rate constants for the reactions of C₂H₆, C₂H₅D and C₂D₆ with .CCl₃. for the production of CHCl₃ and CDCl₃ (k₁, k₂, k₃ and k₄) were computed using variational transition state theory coupled with hybrid-meta density functional theory (MPWB1K) over the temperature range of 200–2900 K. The ground-state vibrational adiabatic potential was plotted for all channels. Small- and large-curvature tunnelling were determined to include quantum effects in the calculation of rate constants. Harmonic vibrational frequencies along the reaction path were calculated in curvilinear coordinates with scaled frequencies. Anharmonicity was included in the lowest-frequency torsion. The position of formation and dissociation of bonds was specified using the variation in harmonic vibrational frequencies along the reaction path. Representative tunnelling energy and the thermally averaged transmission probability at 298 K (P(E)exp?( ? ΔE/RT)) were determined for the reactions in which tunnelling is important. The kinetic isotope effect was used to calculate the considerable contributions of tunnelling and vibration. The expressions for rate constants were determined using nonlinear least-square fitting over the temperature range of 200–2900 K.     

Ab initio investigation of the electronic and vibrational properties for the (CaLi)+ ionic molecule

A wide adiabatic study has been performed for numerous electronic states of CaLi⁺ molecular ion. The adiabatic potential energy curves and their spectroscopic constants (R_e, D_e, ω_e and T_e) have been calculated using an ab initio approach including a nonempirical pseudo-potential for the Ca and Li cores with the core polarisation potentials operator through full configuration interaction (FCI). Thereafter, the energies of vibrational levels and their spacing for all these states have been reported. In addition, the electric dipole moment curves have been investigated for the (1-19) Σ, (1-12) Π and (1-8) Δ electric states. Moreover it lets us check the extreme transition dipole moments (TDM). These behaviours of TDM are more accustomed to estimate the radiative lifetimes for all vibrational levels in 2¹Σ⁺ and 3¹Σ⁺ states. Also, the bound-bound and the bound-free contribution have been calculated precisely and by employing a Franck–Condon (FC) approximation.     

FFT-based convolution algorithm for fast and precise numerical evaluating diffracted field by photon sieve

FFT-based convolution is proposed to numerical solve Fresnel–Kirchhoff integral in Fresnel regime carefully and in a very shorter time in comparison to direct solving convolution. To show its capability, the algorithm was implemented to evaluate amplitude of a diffracted plane wave at the focal plane of photon sieves with different focal lengths. The calculated amplitudes are completely the same calculated via convolving operation but has advantageous of taking very very shorter time. The calculation was also repeated using single-FFT algorithm that produce same result for all ranges either below or upper the sampling criteria and different results in comparison to the other two methods.     

Angular Multiplexing Gratings Characterization in Dichromated Gelatin and Thoughts on Diffractive Optical Memory

We were mainly concerned here with multiple exposure gratings that allow interactions and coupling between gratings. We started the study of interactions and coupling with five gratings recorded in dichromated gelatin (DCG). Having determined experimentally the characteristic parameters of these five gratings, we used a method developed by Oxford University to synthesize the modulation profile. Entering these parameters of each grating into our computing programs (based on the alternative theory of diffraction in modulated media) and by varying the amplitude modulation, the latter was deduced by adjusting the numerical curve to the experimental one. We then extended the study to nine multiplexed gratings. This study allowed us to know the range of the amplitude modulation such that a certain number of angular multiplexing can be done in DCG. Several undesirable effects which we had experimentally observed appeared then during the reconstruction of any one of the multiplexed images, such as cross-talk effect. We noted the good concordance between experimental and theoretical results. We finally illustrated cross-talk effect in a diffractive memory where, if the amplitude modulation was first calculated, the number of multiplexing for an angular range could then be determined and the angular separation achieved to avoid cross-talk.     

A design of fluorescent probes for superoxide based on a nonredox mechanism

Fluorometric detection of O2-* is performed based on desulfonylation of 3 to the corresponding fluoresceins 4 through nucleophilic substitution, and this fluorescing process is quite specific toward O2-* over H2O2, t-BuOOH, NaOCl, 1O2, HO*, NO*, and ONOO-. Furthermore, effects of glutathione, cytochrome P450 reductase/NADPH, and diaphorase/NADH are relatively small on the fluorescing process of probe 3 with X = Y = F, which is useful to detect O2-* released from neutrophils stimulated by phorbol myristate acetate with satisfactory sensitivity.     

Phase transition in ammonium hexafluorovanadate (III)

Heat capacity of ammonium hexafluorovanadate (NH₄)₃ [VF₆] has been measured with a miniaturized adiabatic calorimeter from 20 to 300 K. A phase transition was found at 280.44 ± 0.05 K with the associated entropy change Δ_trs S = 24.9 ± 0.5 JK^?1 mol^?1. The entropy transition is accounted for by the orientational order-disorder changes of hexafluorovanadate ion and ammonium ion occupying respective octahedral sites, as in the cases of (NH₄)₃AlF₆ and (NH₄)₃FeF₆ crystals. Changes in infrared spectra relative to v₃ vibrational mode of [VF₆]^3? ion can be explained by an orientational disorder of the anions in the high-temperature phase (HTP). The dependence of cubic root of the unit-cell volume of a family of ammonium cryolites on their transition temperatures is discussed in relation to the nature of interactions which induce the phase transition.     

The first Chevalley–Eilenberg Cohomology group of the Lie algebra on the transverse bundle of a decreasing family of foliations

In [L. Lebtahi, Lie algebra on the transverse bundle of a decreasing family of foliations, J. Geom. Phys. 60 (2010), 122–133], we defined the transverse bundle V^k$V^k$ to a decreasing family of k$k$ foliations _Fi$F_i$ on a manifold M$M$. We have shown that there exists a (1,1)$(1,1)$ tensor J$J$ of V^k$V^k$ such that J^k≠0$J^k\ne 0$, J^k+1=0$J^{k+1}=0$ and we defined by _LJ(V^k)$L_J\left(V^k\right)$ the Lie Algebra of vector fields X$X$ on V^k$V^k$ such that, for each vector field Y$Y$ on V^k$V^k$, [X,JY]=J[X,Y]$[X,JY]=J[X,Y]$.