Molecular dynamics simulations of liquid water: Voronoi polyhedra and network topology

We have carried out various runs at different temperatures simulating liquid water via the TIP4P model, a well tested and widely used 4-site intermolecular potential. Voronoi polyhedra have been constructed and the distributions of various quantities analyzed. The higher the temperature, the more the distributions are similar to those of a normal liquid: as a reference for a corresponding liquid without hydrogen bonds, we have examined hydrogen sulphide. The typical shape of the Voronoi polyhedra is not too far from the polyhedra of a perfect ice I_h crystal, although the numbers of vertices and faces are almost doubled. Indeed the actual number of vertices increases rapidly toward the liquid value as the crystal is perturbed by thermal motions. It is remarkable that the total surface and volume are always found closely correlated. It denotes a quasi-constant shape, i.e. the various shapes are not dependent on the volume. Indeed a direct analysis shows that there is no correlation between volume and shape. A quantitative characterization of the Voronoi polyhedra shape is proposed, through an “asphericity” parameter, whose distribution is found to be greatly affected by temperature: a net shift of the centre of the curve toward the value for the ice is found as the temperature is lowered. Finally it is found that there is a positive correlation between the potential energy of a molecule and the local volume, thus indicating that the hypothesis that the four-bonded molecules have a local density lower than average is incorrect.     

"Tetrahedrality" and the relationship between collective structure and radial distribution functions in liquid water

Molecular dynamics simulations of pure liquid water under ambient conditions using four common empirical water models have been analyzed to determine how well the oxygen-oxygen radial distribution function, g(OO)(r), used as the sole criterion of congruence with experiment, captures variations in the actual anisotropic collective structuring for these models. The largest systematic deviations from tetrahedrality were found to be due to deformations of the angle between the two closet hydrogen bond donor neighbors, but for intrinsic geometric reasons, these were found to contribute less to g(OO)(r) than deformations of the angles between one hydrogen bond donor neighbor and one hydrogen bond acceptor neighbor. Relying exclusively on a qualitative characterization of the second peak in g(OO)(r) seems to overemphasize the differences between the structuring in some of these models.     

On the origin of the splitting of the second maximum in the radial distribution function of amorphous solids

The splitting of the second maximum of the radial distribution function of an irregular atomic packing is regarded as an indication of the amorphous state of a substance. This paper describes the splitting-forming atomic configurations using Delaunay simplices, representing chains of elementary configurations. It is shown that the splitting is formed of chains in which all simplices are nearly regular tetrahedra and quartoctahedra. Translated fromZhumal Struktumoi Khimii, Vol. 38, No. 1, pp. 78–88, January–February, 1997.     

Intramolecular disorder and its relation to mesophase structure in lyotropic liquid crystals

NMR SPDE measurements are reported for the lamellar (dispersions and multibilayer stacks) and hexagonal phases of sodium octanoate/octanol/D₂O mixtures. In the lamellar L_β and L_γ (gel) phases the octyl chains are rigid and perfectly ordered, while in the lamellar L_α and hexagonal phases they are flexible and disordered. In particular, the measurements show that in the fluid lamellar L_α phase, there is a marked discontinuity in the octyl chain flexibility at the C₅-C₆ segment; this behaviour is identical to that previously reported for the alkyl end-chains in smectic 4,4′-di-n-octyloxyazoxybenzene. In contrast, in the hexagonal phase, there is an effectively continuous flexibility gradient along the whole length of the octyl chain as in nematic 4,4′-di-n-octyloxyazoxybenzene. The behaviour in the lamellar phase is attributed to interference between cooperative conformational modes and localized random thermal fluctuations.     

Shear-induced topology changes in liquid crystals of the soybean lecithin/DDAB/water system

The viscoelastic behavior of the two different liquid crystalline lamellar phases and the liquid crystalline cubic phase of the mixed soybean lecithin/DDAB system in water was studied through rheology, with mechanical parameters studied as a function of composition. The swollen or diluted lamellar region is formed by vesicles, and its characteristic flow curve presents two-power law regions separated by a region where viscosity passes through a maximum. Yield stress and shear-dependent flow behavior were also observed. The microstructure suffers transformation under shear stress, and rheological response shifts from thixotropic to antithixotropic loops. Similar rheological behavior has been observed for samples in the collapsed or concentrated lamellar region, at the water-rich corner of the phase diagram. Vesicle formation may therefore occur by shearing the initial stacked and open bilayers. However, concentrated lamellar samples in the water-poor part of the phase diagram are less sensitive to shear effects and show plastic behavior and thixotropy. All lamellar samples manifest high elasticity. The dynamic responses of both lamellar topologies, i.e., vesicles and open bilayers, are comparable and exhibit an infinite relation time. The bicontinuous cubic, liquid crystalline phase is highly viscous. Its dynamic response cannot be modeled by a Maxwell model.     

Blip function calculation of the radial distribution functions for a binary liquid mixture

It is shown that the use of the high temperature approximation to blip function theory together with a two-component hard sphere reference fluid leads to reasonably accurate predictions for the radial distribution functions in a moderate temperature, moderate density, binary Lennard-Jones mixture.     

Broadband reflective cholesteric liquid crystalline gels: volume distribution of reflection properties and polymer network in relation with the geometry of the cell photopolymerization

The ultraviolet (UV) light‐absorbing properties of the liquid crystal (LC) constituent during the photo‐induced elaboration of a cholesteric LC (CLC) gel may induce the broadening of the reflection bandwidth of the material, a situation that is promoted by asymmetrical irradiation conditions (only one side of the cell is irradiated). The in situ structure of the polymer network, included in the LC, was investigated by transmission electron microscopy and the temperature dependence of the reflection properties examined; it is shown that the network has a structure gradient that is at the origin of the broadening phenomenon. The smallest reflection wavelength is related to the cell side from which the UV light beam came in. A priori, this situation was unexpected since it is shown that this part of the gel is enriched with nematic (infinite‐pitch CLC) network‐forming material. The result is discussed in relation to the variation of the reflection band characteristics with polymer concentration, which offers the opportunity for indirect access to the volume distribution of the cholesteric periodicities. For applications, broadband reflective cholesteric gels may be of interest for reflective polarizer‐free displays or for the light management with smart electrically‐switchable reflective windows.     

Broadband reflective cholesteric liquid crystalline gels: volume distribution of reflection properties and polymer network in relation with the geometry of the cell photopolymerization

The ultraviolet (UV) light-absorbing properties of the liquid crystal (LC) constituent during the photo-induced elaboration of a cholesteric LC (CLC) gel may induce the broadening of the reflection bandwidth of the material, a situation that is promoted by asymmetrical irradiation conditions (only one side of the cell is irradiated). The in situ structure of the polymer network, included in the LC, was investigated by transmission electron microscopy and the temperature dependence of the reflection properties examined; it is shown that the network has a structure gradient that is at the origin of the broadening phenomenon. The smallest reflection wavelength is related to the cell side from which the UV light beam came in. A priori, this situation was unexpected since it is shown that this part of the gel is enriched with nematic (infinite-pitch CLC) network-forming material. The result is discussed in relation to the variation of the reflection band characteristics with polymer concentration, which offers the opportunity for indirect access to the volume distribution of the cholesteric periodicities. For applications, broadband reflective cholesteric gels may be of interest for reflective polarizer-free displays or for the light management with smart electrically-switchable reflective windows.     

An accurate expression for radial distribution function of the Lennard-Jones fluid

A simple and accurate expression for radial distribution function (RDF) of the Lennard-Jones fluid is presented. The expression explicitly states the RDF as a continuous function of reduced interparticle distance, temperature, and density. It satisfies the limiting conditions of zero density and infinite distance imposed by statistical thermodynamics. The distance dependence of this expression is expressed by an equation which contains 11 adjustable parameters. These parameters are fitted to 353 RDF data, obtained by molecular dynamics calculations, and then expressed as functions of reduced distance, temperature and density. This expression, having a total of 65 constants, reproduces the RDF data with an average root-mean-squared deviation of 0.0152 for the range of state variables of 0.5  T^*  5.1 and 0.35  ρ^*  1.1 (T^*=kT/ε and ρ^* = ρσ³ are reduced temperature and density, respectively). The expression predicts the pressure and the internal energy of the Lennard-Jones fluid with an uncertainty that is comparable to that obtained directly from the molecular dynamics simulations.     

On the phase sequence of antiferroelectric liquid crystals and its relation to orientational and translational order

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC* in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC* phase, this phase rapidly replaces the SmC*_β subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investigations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC*β phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC* phase at the cost of the AFLC phases SmC*_α, SmC*_β, SmC*_γ and SmC*_a. We also propose that the SmA* phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA* -SmC*_a transition are found to be typical ‘de Vries smectics’, with very high orientational disorder in the SmA* phase. Finally, we discuss the fact that SmC*_β and SmC*_γ have two superposed helical superstructures and explain the observation that the handedness of the large scale helix may very well change sign, while the handedness on the unit cell level is preserved.     

On the relation between the molecular mass distribution of gelatin and its ability to stabilize emulsions

The relation between the molecular mass distribution of gelatin and its effectiveness in stabilizing emulsions of dibutyl phthalate and dodecane in water have been investigated. The molecular mass distribution was determined using gel permeation chromatography. The ability of gelatin samples to stabilize emulsions was investigated by observing the coalescence of macroscopic oil droplets in a special device. The results show that all samples with a content of more than 30 wt.-% in the low-molecular mass range are good stabilizers, whereas the stabilizing ability is diminished drastically by decreasing the low molecular mass content below 30 wt.-%. Mechanisms for the stabilization and rupture of the thin water film between the oil droplets are discussed, especially in the case of gelatin adsorption layers at the film interfaces. A model is given for the qualitative explanation of the dependence of the stabilizing ability of gelatins on the molecular mass distribution.     

Structural and atoms-in-molecules analysis of hydrogen-bond network around nitroxides in liquid water

In this study, we investigated the hydrogen-bond network patterns involving the NO moieties of five small nitroxides in liquid water by analyzing nanosecond scale molecular dynamics trajectories. To this end, we implemented two types of hydrogen-bond definitions, based on electronic structure, using Bader's atoms-in-molecules analysis and based on geometric criteria. In each definition framework, the nitroxide/water hydrogen-bond networks appear very variable from a nitroxide to another. Moreover, each definition clearly leads to a different picture of nitroxide hydration. For instance, the electronic structure-based definition predicts a number of hydrogen bonds around the nitroxide NO moiety usually larger than geometric structure-based ones. One particularly interesting result is that the strength of a nitroxide/water hydrogen bond does not depend on its linearity, leading us to question the relevance of geometric definition based on angular cutoffs to study this type of hydrogen bond. Moreover, none of the hydrogen-bond definitions we consider in the present study is able to quantitatively correlate the strength of nitroxide/water hydrogen-bond networks with the aqueous nitroxide spin properties. This clearly exhibits that the hydrogen-bonding concept is not reliable enough to draw quantitative conclusions concerning such properties.     

Degradation study of benomyl and carbendazim in water by liquid chromatography and multivariate curve resolution methods

Summary The degradation of benomyl and carbendazim in different organic solvents, distilled and ground waters was studied by on-line solid-phase extraction (SPE) followed by liquid chromatography (LC), diode array detection (DAD) or atmospheric pressure chemicalionization mass spectrometry detection (APCI-MS), UV spectrophotometry and multivariate curve resolution. Stability studies were performed in different organic solvents, such as acetonitrile and methanol, and in aqueous solution at different pH. Samples were stored in dark conditions at 4 °C and analysed by LC-DAD over 10 days. Photodegradation products of benomyl were resolved by spectrophotometry and multivariate curve resolution between pH 3 to 9. These results were correlated with those from LC-DAD and LC-APCI-MS. Photolysis studies were carried out at low concentration levels (2 μg L⁻¹) of carbendazim under different storage conditions in order to evaluate the effect of parameters, such as pH, temperature and sunlight exposure. Water samples (50 mL) were preconcentrated using on-line SPEC-LC-DAD. Photodegradation products of benomyl and carbendazim were identified by on-line-SPE-LC-DAD and SPE-LC-APCI-MS, leading to identification DAD and SPE-LC-APCI-MS, leading to identification of carbendazim, 3-butyl-2,4-dioxo-s-triazino1,2-abenzimidazole (STB) and 2-aminobenzimidazole (2-AB). Dedicated to Professor W. Haerdi on the occasion of his 70^th birthday.