SAFT-γ Force Field for the Simulation of Molecular Fluids 6. Binary and ternary mixtures comprising water, carbon dioxide, and n-alkanes

AbstractThe SAFT-γ coarse graining methodology (Avendaño et al., 2011) is used to develop force fields for the fluid-phase behaviour of binary and ternary mixtures comprising water, carbon dioxide, and n-alkanes. The effective intermolecular interactions between the coarse grained (CG) segments are directly related to macroscopic thermodynamic properties by means of the SAFT-γ equation of state for molecular segments represented with the Mie (generalised Lennard–Jones) intermolecular potential (Papaioannou et al., 2014). The unlike attractive interactions between the components of the mixtures are represented with a single adjustable parameter, which is shown to be transferable over a wide range of conditions. The SAFT-γ Mie CG force fields are used in molecular-dynamics simulations to predict the challenging (vapour+liquid) and (liquid+liquid) fluid-phase equilibria characterising these mixtures, and to study phenomena that are not accessible directly from the equation of state, such as the interfacial properties. The description of the fluid-phase equilibria and interfacial properties predicted with the SAFT-γ Mie force fields is in excellent agreement with the corresponding experimental data, and of comparable if not superior quality to that reported for the more sophisticated atomistic and united-atom models

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

Carbon Monoxide Screening in Pregnancy: An Evaluation Study of a Plymouth Pilot Intervention

This report provides an analysis and evaluation of a National Institute for Health and Care Excellence (NICE) recommended pilot intervention which was designed to identify pregnant women exposed to carbon monoxide due to cigarette smoke and refers them to local stop smoking services (LSSS). The pilot intervention was carried out by community midwives working in two areas of Plymouth. The city has areas of social and health inequalities and the study drew on populations from a socially deprived neighbourhood and a socially affluent area. The pilot was instigated following new NICE guidance recommending that all women attending initial ante natal booking appointments with their community midwives be offered a Carbon Monoxide (CO) breath analyser screening to determine their smoking status and or exposure to other forms of CO. This evaluation study identifies the benefits and barriers associated with the implementation of the CO screening pilot. In particular, our aims were to explore any detrimental impact on the relationship between women and their community midwives, identify the impact on midwives in terms of time and resources, reveal the responses and acceptability or otherwise of the screening as perceived and experienced by the women being asked to participate during the booking appointment and finally to evaluate the success of the intervention overall in relation to the numbers of referrals made to Plymouth’s LSSS. A further aim was explore any differences in the two socio demographic areas. We adopted a mixed methods approach involving four focus group interviews with 23 midwives, a survey posted to the 258 women who attended initial antenatal booking appointments in the study areas, an online version of the survey to ascertain the views and experiences of pregnant women and new mothers nationally and an interrogation of an internet forum discussion board for mothers. A two page questionnaire consisting of 12 questions was designed and posted to women who attended the booking appointment with the midwife during the three month pilot period and the same survey was made available online. Questions were designed to elicit women’s views about the information given by the midwife in relation to the screening, whether they had agreed to participate in the CO screening process, their experiences and views about offering CO screening to pregnant women and their smoking status and those of other household members. Of the 258 questionnaires posted to women who had attended the clinic during the pilot intervention 40 completed responses were returned representing a 15.5% response rate. Only 4 responses were received from the online survey posting but an additional 484 comments posted on the Mumsnet website discussion board were analysed. Our findings show that in general there was a high degree of acceptability for the intervention. Midwives and their clients were generally in support of the screening being offered to all pregnant women. However, this support was dependent on a number of contextual factors. Women wanted to be properly informed about the screening and midwives wanted to be kept informed about the effects of the intervention on women’s smoking cessation. Initial and ongoing training of midwives in utilising the protocol and in instructing women to correct use the monitor was also very important. Trust was revealed to be a very important aspect of the relationship between women and their midwives. Some women felt that the CO screening was being used just to check whether or not they were smokers and some midwives also worried about the possible negative effects the CO screening may have on their relationships with women

SAFT-γ force field for the simulation of molecular fluids: 8. hetero-group coarse-grained models of perfluoroalkylalkanes assessed with new vapour-liquid interfacial tension data

The air-liquid interfacial behaviour of linear perfluoroalkylalkanes (PFAAs) is reported through a combined experimental and computer simulation study. The surface tensions of seven liquid PFAAs (perfluorobutylethane, F4H2; perfluorobutylpentane, F4H5; perfluorobutylhexane, F4H6, perfluorobutyloctane, F4H8; perfluorohexylethane, F6H2; perfluorohexylhexane, F6H6; and perfluorohexyloctane, F6H8) are experimentally determined over a wide temperature range (276 to 350 K). The corresponding surface thermodynamic properties and the critical temperatures of the studied compounds are estimated from the temperature dependence of the surface tension. Experimental density and vapour pressure data are employed to parameterize a generic heteronuclear coarse-grained intermolecular potential of the SAFT- γ family for PFAAs. The resulting force field is used in direct molecular dynamics simulations to predict with quantitative agreement the experimental tensions and to explore the conformations of the molecules in the interfacial region revealing a preferential alignment of the PFAA molecules towards the interface and an enrichment of the perfluoro-groups at the outer interface region

Domain walls and instantons in N=1, d=4 supergravity

We study the supersymmetric sources of (multi-) domain-wall and (multi-) instanton solutions of generic N=1, d=4 supergravities, that is: the worldvolume effective actions for said supersymmetric topological defects. The domain-wall solutions naturally couple to the two 3-forms recently found as part of the N=1, d=4 tensor hierarchy (i.e. they have two charges in general) and their tension is the absolute value of the superpotential section L. The introduction of sources (we study sources with finite and vanishing thickness) is equivalent to the introduction of local coupling constants and results in dramatic changes of the solutions. Our results call for a democratic reformulation of N=1,d=4 supergravity in which coupling constants are, off-shell, scalar fields. The effective actions for the instantons are always proportional to the coordinate orthogonal to the twist-free embedding of the null-geodesic (in the Wick-rotated scalar manifold) describing the instanton. We show their supersymmetry and find the associated supersymmetric (multi-) instanton solutions.Comment: 34 pages, 4 figures, references adde

The kinetic MC modelling of reversible pattern formation in initial stages of thin metallic film growth on crystalline substrates

The results of kinetic MC simulations of the reversible pattern formation during the adsorption of mobile metal atoms on crystalline substrates are discussed. Pattern formation, simulated for submonolayer metal coverage, is characterized in terms of the joint correlation functions for a spatial distribution of adsorbed atoms. A wide range of situations, from the almost irreversible to strongly reversible regimes, is simulated. We demonstrate that the patterns obtained are defined by a key dimensionless parameter: the ratio of the mutual attraction energy between atoms to the substrate temperature. Our ab initio calculations for the nearest Ag-Ag adsorbate atom interaction on an MgO substrate give an attraction energy as large as 1.6 eV, close to that in a free molecule. This is in contrast to the small Ag adhesion and migration energies (0.23 and 0.05 eV, respectively) on a defect-free MgO substrate. (C) 2003 Elsevier Science Ltd. All rights reserved

First principles simulations of 2D Cu superlattices on the MgO(001) surface

First principles slab simulations of copper 2D superlattices of different densities on the perfect MgO(0 0 1) surface are performed using the DFT method as implemented into the CRYSTAL98 computer code. In order to clarify the nature of interfacial bonding, we consider regular 1/4, 1/2 and I monolayer (ML) coverages and compare results of our calculations with various experimental and theoretical data. Our general conclusion is that the physical adhesion associated with a Cu polarization and charge redistribution gives the predominant contribution to the bonding of the regular Cu 2D layer on the MgO(0 0 1) surface. (C) 2003 Elsevier B.V. All rights reserved

SAFT-γ force field for the simulation of molecular fluids: 4. A single-site coarse-grained model of water applicable over a wide temperature range

In this work, we develop coarse-grained (CG) force fields for water, where the effective CG intermolecular interactions between particles are estimated from an accurate description of the macroscopic experimental vapour-liquid equilibria data by means of a molecular-based equation of state. The statistical associating fluid theory for Mie (generalised Lennard-Jones) potentials of variable range (SAFT-VR Mie) is used to parameterise spherically symmetrical (isotropic) force fields for water. The resulting SAFT-γ CG models are based on the Mie (8-6) form with size and energy parameters that are temperature dependent; the latter dependence is a consequence of the angle averaging of the directional polar interactions present in water. At the simplest level of CG where a water molecule is represented as a single bead, it is well known that an isotropic potential cannot be used to accurately reproduce all of the thermodynamic properties of water simultaneously. In order to address this deficiency, we propose two CG potential models of water based on a faithful description of different target properties over a wide range of temperatures: our CGW1-vle model is parameterised to match the saturated-liquid density and vapour pressure; our other CGW1-ift model is parameterised to match the saturated-liquid density and vapour-liquid interfacial tension. A higher level of CG corresponding to two water molecules per CG bead is also considered: the corresponding CGW2-bio model is developed to reproduce the saturated-liquid density and vapour-liquid interfacial tension in the physiological temperature range, and is particularly suitable for the large-scale simulation of bio-molecular systems. A critical comparison of the phase equilibrium and transport properties of the proposed force fields is made with the more traditional atomistic models

NAFLD: Diagnostic Algorithms for Regulating Patient Fluxes

The global prevalence of NAFLD is estimated to be over 25% and it is already the leading cause of chronic liver disease in industrialized countries, as a consequence of the spread of obesity and metabolic syndrome. The prognosis of NAFLD is generally benign in the absence of fibrosis, but liver fibrosis rapidly progresses in 20% of the cases and can lead to cirrhosis and/or HCC. This review analysis focuses on non-invasive fibrosis testing strategies for patients with NAFLD in order to increase the efficiency and effectiveness of diagnosis and care, regulating secondary care referral fluxes. An integrated management plan between primary care and secondary care with a defined algorithm of non-invasive testing to stratify the risk of NAFLD fibrosis is indispensable to increase the early diagnosis of fibrosis but also decrease unnecessary referrals