The Many Faces of Heterogeneous Ice Nucleation: Interplay Between Surface Morphology and Hydrophobicity

What makes a material a good ice nucleating agent? Despite the importance of heterogeneous ice nucleation to a variety of fields, from cloud science to microbiology, major gaps in our understanding of this ubiquitous process still prevent us from answering this question. In this work, we have examined the ability of generic crystalline substrates to promote ice nucleation as a function of the hydrophobicity and the morphology of the surface. Nucleation rates have been obtained by brute-force molecular dynamics simulations of coarse-grained water on top of different surfaces of a model fcc crystal, varying the water-surface interaction and the surface lattice parameter. It turns out that the lattice mismatch of the surface with respect to ice, customarily regarded as the most important requirement for a good ice nucleating agent, is at most desirable but not a requirement. On the other hand, the balance between the morphology of the surface and its hydrophobicity can significantly alter the ice nucleation rate and can also lead to the formation of up to three different faces of ice on the same substrate. We have pinpointed three circumstances where heterogeneous ice nucleation can be promoted by the crystalline surface: (i) the formation of a water overlayer that acts as an in-plane template; (ii) the emergence of a contact layer buckled in an ice-like manner; and (iii) nucleation on compact surfaces with very high interaction strength. We hope that this extensive systematic study will foster future experimental work aimed at testing the physiochemical understanding presented herein.Comment: Main + S

Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations

The nucleation of crystals in liquids is one of nature's most ubiquitous phenomena, playing an important role in areas such as climate change and the production of drugs. As the early stages of nucleation involve exceedingly small time and length scales, atomistic computer simulations can provide unique insight into the microscopic aspects of crystallization. In this review, we take stock of the numerous molecular dynamics simulations that in the last few decades have unraveled crucial aspects of crystal nucleation in liquids. We put into context the theoretical framework of classical nucleation theory and the state of the art computational methods, by reviewing simulations of e.g. ice nucleation or crystallization of molecules in solutions. We shall see that molecular dynamics simulations have provided key insight into diverse nucleation scenarios, ranging from colloidal particles to natural gas hydrates, and that in doing so the general applicability of classical nucleation theory has been repeatedly called into question. We have attempted to identify the most pressing open questions in the field. We believe that by improving (i.) existing interatomic potentials; and (ii.) currently available enhanced sampling methods, the community can move towards accurate investigations of realistic systems of practical interest, thus bringing simulations a step closer to experiments

Communication: Truncated non-bonded potentials can yield unphysical behavior in molecular dynamics simulations of interfaces

Non-bonded potentials are included in most force fields and therefore widely used in classical molecular dynamics simulations of materials and interfacial phenomena. It is commonplace to truncate these potentials for computational efficiency based on the assumption that errors are negligible for reasonable cutoffs or compensated for by adjusting other interaction parameters. Arising from a metadynamics study of the wetting transition of water on a solid substrate, we find that the influence of the cutoff is unexpectedly strong and can change the character of the wetting transition from continuous to first order by creating artificial metastable wetting states. Common cutoff corrections such as the use of a force switching function, a shifted potential, or a shifted force do not avoid this. Such a qualitative difference urges caution and suggests that using truncated non-bonded potentials can induce unphysical behavior that cannot be fully accounted for by adjusting other interaction parameters

Solubility and activity of oxygen in liquid germanium and germanium-copper alloys

The solubility of oxygen in liquid germanium in the temperature range 1233 to 1397 K, and in liquid germanium-copper alloys at 1373 K, in equilibrium with GeO2 has been measured by the phase equilibration technique. The solubility of oxygen in pure germanium is given by the relation 6470 log(at, pct 0) =-6470/T + 4.24 (±0.07). The standard free energy of solution of oxygen in liquid germanium is calculated from the saturation solubility, and recently measured values for the free energy of formation of GeO2, assuming that oxygen obeys Sievert's law up to the saturation limit. For the reaction, ½O2(g)→OGe ΔG ° =-39,000 + 3.21 T ( ±500) ca1 = -163,200 + 13.43 T (±2100) J. where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct), in the limit, as concentration approaches zero. The effect of copper on the activity of oxygen dissolved in liquid germanium is found to be in good agreement with that predicted by a quasichemical model in which each oxygen was assumed to be bonded to four metal atoms and the nearest neighbor metal atoms to an oxygen atom are assumed to lose approximately half of their metallic bonds

Activities in the spinel solid solution, phase equilibria and thermodynamic properties of ternary phases in the system Cu-Fe-0

A review of the structural and thermodynamic information and phase equilibria in the Cu-Fe-O system suggested that a consistent, quantitative description of the system is hampered by lack of data on activities in the spinel solid solution CuFe2O4-Fe3O4. Therefore the activity of Fe3O4 in this solid solution is derived from measurements of the oxygen potentials established at 1000°C by mixtures containing Fe2O3 and spinel solid solutions of known composition. The oxygen pressures were measured manometrically for solid solutions rich in CuFe2O4, while for Fe3O4-rich compositions the oxygen potentials were obtained by an emf technique. The activities show significant negative deviations from Raoult's law. The compositions of the spinel solid solutions in equilibrium with CuO + CuFeO2 and Cu + CuFeO2 were obtained from chemical analysis of the solid solution after magnetic separation. The oxygen potential of the three-phase mixture Cu + CuFeO2 + Fe3O4(spinel s.s.) was determined by a solid oxide galvanic cell. From these measurements a complete phase diagram and consistent thermodynamic data on the ternary condensed phases, CuFeO2 and CuFeO2O4, were obtained. An analysis of the free energy of mixing of the spinel solid solution furnished information on the distribution of cations and their valencies between the tetrahedral and octahedral sites of the spinel lattice, which is consistent with X-ray diffraction, magnetic and Seebeck coefficient measurements

Ice is born in low-mobility regions of supercooled liquid water.

When an ice crystal is born from liquid water, two key changes occur: (i) The molecules order and (ii) the mobility of the molecules drops as they adopt their lattice positions. Most research on ice nucleation (and crystallization in general) has focused on understanding the former with less attention paid to the latter. However, supercooled water exhibits fascinating and complex dynamical behavior, most notably dynamical heterogeneity (DH), a phenomenon where spatially separated domains of relatively mobile and immobile particles coexist. Strikingly, the microscopic connection between the DH of water and the nucleation of ice has yet to be unraveled directly at the molecular level. Here we tackle this issue via computer simulations which reveal that (i) ice nucleation occurs in low-mobility regions of the liquid, (ii) there is a dynamical incubation period in which the mobility of the molecules drops before any ice-like ordering, and (iii) ice-like clusters cause arrested dynamics in surrounding water molecules. With this we establish a clear connection between dynamics and nucleation. We anticipate that our findings will pave the way for the examination of the role of dynamical heterogeneities in heterogeneous and solution-based nucleation

Global seasonal influenza mortality estimates:a comparison of three different approaches

Prior to updating global influenza-associated mortality estimates, the World Health Organization convened a consultation in July 2017 to understand differences in methodology and implications for results of 3 influenza mortality projects from the US Centers for Disease Control and Prevention (CDC), the Netherlands Institute for Health Service Research’s Global Pandemic Mortality Project II (GLaMOR), and the Institute for Health Metrics and Evaluation (IHME). The expert panel reviewed estimates and discussed differences in data sources, analysis, and modeling assumptions. We performed a comparison analysis of the estimates. Influenza-associated respiratory death counts were comparable between CDC and GLaMOR; the IHME estimate was considerably lower. The greatest country-specific influenza-associated fold differences in mortality rate between CDC and IHME estimates and between GLaMOR and IHME estimates were among countries in Southeast Asia and the Eastern Mediterranean region. The data envelope used for the calculation was one of the major differences (CDC and GLaMOR: all respiratory deaths; IHME: lower-respiratory infection deaths). With the assumption that there is only one cause of death for each death, IHME estimates a fraction of the full influenza-associated respiratory mortality that is measured by the other 2 groups. Wide variability of parameters was observed. Continued coordination between groups could assist with better understanding of methodological differences and new approaches to estimating influenza deaths globally

Effects of Feeding Increasing Levels of HP 300 on Nursery Pig Performance

A total of 1,215 pigs (PIC 337 × 1050; initial BW 11.3 lb) were used in a 43-d growth trial evaluating the effects of feeding increasing HP 300 (Hamlet Protein, Findlay, OH) on nursery pig performance. Pigs were weaned at 16 to 19 d of age and placed in pens, with each pen containing a mix of barrows and gilts. Pens of pigs were weighed and allotted by BW to 1 of 5 dietary treatments in a randomized complete block design with 27 pigs per pen and 9 pens per treatment. The control diet was a standard cornsoybean meal-based diet with 7.5 and 5.63% fish meal (FM) included in phases 1 and 2, respectively. First, the diet with the highest inclusion of HP 300 (phase 1 – 20%; phase 2 – 15%) was formulated and 2 intermediate diets (low and medium HP 300) were then created to have an equal stepwise increase in HP 300 with the HP 300 included at the expense of soybean meal and fish meal. A fifth treatment was then formulated to have the same amount of soybean meal as the control diet, with HP 300 replacing fish meal. From d 22 to 43, a common phase 3 diet was fed to all pigs. Phase 1 diets were fed in pellet form, while phases 2 and 3 were fed in meal form. From d 0 to 7 (phase 1), increasing HP 300 at the expense of soybean meal and fish meal decreased ADFI (quadratic, P = 0.001) in pigs fed the low HP 300 diet, but then increased as HP 300 was increased. No differences were observed for ADG or F/G. Furthermore, performance did not differ between pigs fed the fish meal control diet and pigs fed the diet with HP 300 replacing fish meal. During phase 2 (d 7 to 22), ADG and ADFI decreased (linear, P \u3c 0.05) as HP 300 increased at the expense of soybean meal and fish meal resulting in a tendency for poorer F/G (quadratic, P = 0.073). However, no differences were observed between pigs fed the fish meal control diet and pigs fed HP 300 replacing fish meal. For the entire period when the specialty protein sources were fed (d 0 to 22), pigs fed increasing HP 300 had poorer ADG, ADFI, and final BW (linear, P \u3c 0.05) as HP 300 increased, but there were no differences observed for F/G. In addition, there were no differences observed between pigs fed the fish meal control diet and pigs fed the HP 300 diet replacing fish meal. From d 22 to 43 (phase 3) when a common diet was fed, F/G tended (quadratic, P = 0.075) to improve as HP 300 increased in the previous diets with pigs previously fed the diet with the low inclusion of HP 300 having the best F/G. Overall (d 0 to 43), pigs fed increasing HP 300 had a tendency for poorer ADFI (linear, P = 0.071) resulting in a decreased final BW (linear, P = 0.043). However, no differences were observed for growth performance between pigs fed the fish meal control diet and pigs fed HP 300 replacing fish meal. For the economic analysis, feed cost per pig and cost per pound of gain decreased (linear, P \u3c 0.05) for pigs fed increasing HP 300. However, there were no differences detected for revenue per pig and income over feed cost. In conclusion, increasing HP 300 up to 15 to 20% of the diet for the first 22 d post-weaning at the expense of soybean meal and fish meal resulted in a decrease in final BW at the end of the nursery period

Orbital redistribution in molecular nanostructures mediated by metal-organic bonds

Dicyanovinyl-quinquethiophene (DCV5T-Me) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/STS) and atomic force microscopy (AFM). We find that DCV5T-Me self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal-ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites

Universal finite-size scaling for percolation theory in high dimensions

We present a unifying, consistent, finite-size-scaling picture for percolation theory bringing it into the framework of a general, renormalization-group-based, scaling scheme for systems above their upper critical dimensions $d_c$. Behaviour at the critical point is non-universal in $d>d_c=6$ dimensions. Proliferation of the largest clusters, with fractal dimension $4$, is associated with the breakdown of hyperscaling there when free boundary conditions are used. But when the boundary conditions are periodic, the maximal clusters have dimension $D=2d/3$, and obey random-graph asymptotics. Universality is instead manifest at the pseudocritical point, where the failure of hyperscaling in its traditional form is universally associated with random-graph-type asymptotics for critical cluster sizes, independent of boundary conditions.Comment: Revised version, 26 pages, no figure