Evaluation of Model Concepts to Describe Water Transport in Shallow Subsurface Soil and Across the Soil–Air Interface

Soil water evaporation plays a critical role in mass and energy exchanges across the land–atmosphere interface. Although much is known about this process, there is no agreement on the best modeling approaches to determine soil water evaporation due to the complexity of the numerical modeling scenarios and lack of experimental data available to validate such models. Existing studies show numerical and experimental discrepancies in the evaporation behavior and soil water distribution in soils at various scales, driving us to revisit the key process representation in subsurface soil. Therefore, the goal of this work is to test different mathematical formulations used to estimate evaporation from bare soils to critically evaluate the model formulations, assumptions and surface boundary conditions. This comparison required the development of three numerical models at the REV scale that vary in their complexity in characterizing water flow and evaporation, using the same modeling platform. The performance of the models was evaluated by comparing with experimental data generated from a soil tank/boundary layer wind tunnel experimental apparatus equipped with a sensor network to continuously monitor water–temperature–humidity variables. A series of experiments were performed in which the soil tank was packed with different soil types. Results demonstrate that the approaches vary in their ability to capture different stages of evaporation and no one approach can be deemed most appropriate for every scenario. When a proper top boundary condition and space discretization are defined, the Richards equation-based models (Richards model and Richards vapor model) can generally capture the evaporation behaviors across the entire range of soil saturations, comparing well with the experimental data. The simulation results of the non-equilibrium two-component two-phase model which considers vapor transport as an independent process generally agree well with the observations in terms of evaporation behavior and soil water dynamics. Certain differences in simulation results can be observed between equilibrium and non-equilibrium approaches. Comparisons of the models and the boundary layer formulations highlight the need to revisit key assumptions that influence evaporation behavior, highlighting the need to further understand water and vapor transport processes in soil to improve model accuracy.

     

Analysis of several subcycling schemes in partitioned simulations of a strongly coupled fluid-structure interaction

Fluid-structure interaction (FSI) simulations are used extensively to calculate the vibration of structures subjected to an internal or external flow. In the case of partitioned FSI simulations, separate flow and structure solvers are used, which requires some kind of coupling between both. The time step in both solvers is typically taken the same, but this unnecessarily leads to long calculation times when the time step is small due to stability reasons in one of the two solvers. Subcycling, the procedure where the time step of one solver is chosen smaller than the time step used in the other solver, may reduce the computational cost of the FSI simulation. The subcycling procedure can be either explicit or implicit, the latter implying the use of coupling iterations in each time step. Contrary to explicit subcycling, no stability analyses of implicit subcycling schemes are found in the literature. In this paper, the temporal stability of the implicit subcycling procedure is investigated. The one-dimensional flow in an elastic cylindrical tube is studied analytically. The results of this analysis are subsequently compared to a partitioned two-dimensional axisymmetric FSI calculation with implicit coupling between the flow and structure solvers.     

Colourings of cubic graphs inducing isomorphic monochromatic subgraphs

A -bisection of a bridgeless cubic graph is a -colouring of its vertex set such that the colour classes have the same cardinality and all connected components in the two subgraphs induced by the colour classes ( monochromatic components in what follows) have order at most . Ban and Linial Conjectured that every bridgeless cubic graph admits a -bisection except for the Petersen graph. A similar problem for the edge set of cubic graphs has been studied: Wormald conjectured that every cubic graph with has a -edge colouring such that the two monochromatic subgraphs are isomorphic linear forests (ie, a forest whose components are paths). Finally, Ando conjectured that every cubic graph admits a bisection such that the two induced monochromatic subgraphs are isomorphic. In this paper, we provide evidence of a strong relation of the conjectures of Ban-Linial and Wormald with Ando's Conjecture. Furthermore, we also give computational and theoretical evidence in their support. As a result, we pose some open problems stronger than the above-mentioned conjectures. Moreover, we prove Ban-Linial's Conjecture for cubic-cycle permutation graphs. As a by-product of studying -edge colourings of cubic graphs having linear forests as monochromatic components, we also give a negative answer to a problem posed by Jackson and Wormald about certain decompositions of cubic graphs into linear forests.     

Asymmetric Carboxycyanation of Aldehydes by Cooperative AlF/Onium Salt Catalysts: from Cyanoformate to KCN as Cyanide Source

Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 10⁴. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results.     

Ends,tangles and critical vertex sets

We show that an arbitrary infinite graph G can be compactified by its ends plus its critical vertex sets, where a finite set X of vertices of an infinite graph is critical if its deletion leaves some infinitely many components each with neighbourhood precisely equal to X. We further provide a concrete separation system whose ?₀‐tangles are precisely the ends plus critical vertex sets. Our tangle compactification is a quotient of Diestel's (denoted by ), and both use tangles to compactify a graph in much the same way as the ends of a locally finite and connected graph compactify it in its Freudenthal compactification. Finally, generalising both Diestel's construction of and our construction of , we show that G can be compactified by every inverse limit of compactifications of the sets of components obtained by deleting a finite set of vertices. Diestel's is the finest such compactification, and our is the coarsest one. Both coincide if and only if all tangles are ends. This answers two questions of Diestel.     

A Tunable,Fullerene-Based Molecular Amplifier for Vibrational Circular Dichroism

Vibrational circular dichroism (VCD) studies are reported on a chiral compound in which a fullerene C₆₀ moiety is used as an electron acceptor and local VCD amplifier for an alanine-based peptide chain. Four redox states are investigated in this study, of which three are reduced species that possess low-lying electronic states as confirmed by UV/Vis spectroelectrochemistry. VCD measurements in combination with (TD)DFT calculations are used to investigate (i) how the low-lying electronic states of the reduced species modulate the amplification of VCD signals, (ii) how this amplification depends on the distance between oscillator and amplifier, and (iii) how the spatial extent of the amplifier influences amplification. These results pave the way for further development of tailored molecular VCD amplifiers.