Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics

Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the "mitosis" or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study

Hydrophosphination of styrene and polymerization of vinylpyridine: a computational investigation of calcium-catalyzed reactions and the role of fluxional noncovalent interactions

A computational investigation of the intermolecular hydrophosphination of styrene and 2-vinylpyridine, catalyzed by the heteroleptic β-diketiminato-stabilized calcium complex [(PhNC(Me)CHC(Me)NPh)CaPPh2], is presented. Alkene insertion does not proceed via the traditional route as proposed by experimental and theoretical research related to intermolecular hydroamination catalyzed by alkaline earth or lanthanide complexes. In contrast, for the hydrophosphination mechanism, insertion proceeds via outer sphere, conjugative addition where there is no direct interaction of Ca with the vinyl functionality. Following the initial rate-determining alkene insertion, two distinct mechanisms emerge, protonolysis or polymerization. Polymerization of styrene is energetically less favorable than protonolysis, whereas the reverse is determined for 2-vinylpyridine, thereby providing strong evidence of outcomes observed experimentally. The vinylarene ring is important as it allows for preferential coordination of the unsaturated substrate through numerous noncovalent Ca···π, CH···π, and Ca ← E (E = P or N) interactions; moreover, the vinylarene ring counteracts unfavorable charge localization within the activated transition state. The additional stability of the Ca ← N over Ca ← P dative interaction in vinylpyridine provides a rationalization for the experimentally observed enhanced reactivity of vinylpyridine, particularly in the context of the almost identical local alkene insertion barriers. Previously, little emphasis has been placed on the involvement of noncovalent interactions; however, our calculations reveal that Ca···π, CH···π, and Ca ← donor interactions are critical, stabilizing key intermediates and transition states, while also introducing numerous competitive pathways

Azoniaspiro salts: towards bridging the gap between room-temperature ionic liquids and molten salts.

In a continued effort to improve the suitability of ionic liquids in applications operating at raised temperatures, novel spirocyclic 'azoniaspiro' salts (with cations derived from five-, six-, seven-and eight-membered rings) are prepared and characterised. The structural and thermal properties of these salts are compared against those of established analogues. The stable geometries and ion pairing behaviour of these species are investigated via a combined experimental/computational approach, employing X-ray crystallography and Density Functional Theory (DFT) methods. Subsequently, the thermal stabilities of these organic salts are characterised and compared using a broad range of techniques. Hyphenated Thermogravimetry-Mass Spectrometry investigations enable complex mechanisms underlying thermal decomposition to be elucidated. Lastly, transition state structures are optimised, corresponding to plausible decomposition mechanisms of the azoniaspiro salt, 6-azoniaspiro[6.5]dodecanium chloride, and one prototypical monocyclic species 1-butyl-1-methylpiperidinium chloride, using DFT. The observed improved thermal stabilities of the azoniaspiro salts, and their potential higher-temperature stable-liquid ranges, render them promising candidates for future ionic liquid applications

What's in the Gift? Towards a Molecular Dissection of Nuptial Feeding in a Cricket.

Journal ArticleResearch Support, Non-U.S. Gov'tResearch Support, U.S. Gov't, Non-P.H.S.Nuptial gifts produced by males and transferred to females during copulation are common in insects. Yet, their precise composition and subsequent physiological effects on the female recipient remain unresolved. Male decorated crickets Gryllodes sigillatus transfer a spermatophore to the female during copulation that is composed of an edible gift, the spermatophylax, and the ampulla that contains the ejaculate. After transfer of the spermatophore, the female detaches the spermatophylax and starts to eat it while sperm from the ampulla are evacuated into the female reproductive tract. When the female has finished consuming the spermatophylax, she detaches the ampulla and terminates sperm transfer. Hence, one simple function of the spermatophylax is to ensure complete sperm transfer by distracting the female from prematurely removing the ampulla. However, the majority of orally active components of the spermatophylax itself and their subsequent effects on female behavior have not been identified. Here, we report the first analysis of the proteome of the G. sigillatus spermatophylax and the transcriptome of the male accessory glands that make these proteins. The accessory gland transcriptome was assembled into 17,691 transcripts whilst about 30 proteins were detected within the mature spermatophylax itself. Of these 30 proteins, 18 were encoded by accessory gland encoded messages. Most spermatophylax proteins show no similarity to proteins with known biological functions and are therefore largely novel. A spermatophylax protein shows similarity to protease inhibitors suggesting that it may protect the biologically active components from digestion within the gut of the female recipient. Another protein shares similarity with previously characterized insect polypeptide growth factors suggesting that it may play a role in altering female reproductive physiology concurrent with fertilization. Characterization of the spermatophylax proteome provides the first step in identifying the genes encoding these proteins in males and in understanding their biological functions in the female recipient.Max Planck GesellschaftNational Science FoundationBBSRRoyal Societ

Surface thermodynamics of planar, cylindrical, and spherical vapour-liquid interfaces of water.

The test-area (TA) perturbation approach has been gaining popularity as a methodology for the direct computation of the interfacial tension in molecular simulation. Though originally implemented for planar interfaces, the TA approach has also been used to analyze the interfacial properties of curved liquid interfaces. Here, we provide an interpretation of the TA method taking the view that it corresponds to the change in free energy under a transformation of the spatial metric for an affine distortion. By expressing the change in configurational energy of a molecular configuration as a Taylor expansion in the distortion parameter, compact relations are derived for the interfacial tension and its energetic and entropic components for three different geometries: planar, cylindrical, and spherical fluid interfaces. While the tensions of the planar and cylindrical geometries are characterized by first-order changes in the energy, that of the spherical interface depends on second-order contributions. We show that a greater statistical uncertainty is to be expected when calculating the thermodynamic properties of a spherical interface than for the planar and cylindrical cases, and the evaluation of the separate entropic and energetic contributions poses a greater computational challenge than the tension itself. The methodology is employed to determine the vapour-liquid interfacial tension of TIP4P/2005 water at 293 K by molecular dynamics simulation for planar, cylindrical, and spherical geometries. A weak peak in the curvature dependence of the tension is observed in the case of cylindrical threads of condensed liquid at a radius of about 8 Å, below which the tension is found to decrease again. In the case of spherical drops, a marked decrease in the tension from the planar limit is found for radii below ∼ 15 Å; there is no indication of a maximum in the tension with increasing curvature. The vapour-liquid interfacial tension tends towards the planar limit for large system sizes for both the cylindrical and spherical cases. Estimates of the entropic and energetic contributions are also evaluated for the planar and cylindrical geometries and their magnitudes are in line with the expectations of our simple analysis

What a difference a term makes:the effect of educational attainment on marital outcomes in the UK

Abstract In the past, students in England and Wales born within the first 5 monthsof the academic year could leave school one term earlier than those born later inthe year. Focusing on women, those who were required to stay on an extra termmore frequently hold some academic qualification. Using having been required tostay on as an exogenous factor affecting academic attainment, we find that holding alow-level academic qualification has no effect on the probability of being currentlymarried for women aged 25 or above, but increases the probability of the husbandholding some academic qualification and being economically active.33 Halama

Doppler broadening of in-flight positron annihilation radiation due to electron momentum

An overview is given on the first observation of Doppler broadening due to electron momentum in the τ rays emitted from in-flight two-photon annihilation when highly energetic positrons traverse thin foils. This observation can serve as basis in the development of a new probe of electron momentum distributions similar to Compton or electron scattering technique