Soft matter physics of the ground beneath our feet.

The soft part of the Earth's surface - the ground beneath our feet - constitutes the basis for life and natural resources, yet a general physical understanding of the ground is still lacking. In this critical time of climate change, cross-pollination of scientific approaches is urgently needed to better understand the behavior of our planet's surface. The major topics in current research in this area cross different disciplines, spanning geosciences, and various aspects of engineering, material sciences, physics, chemistry, and biology. Among these, soft matter physics has emerged as a fundamental nexus connecting and underpinning many research questions. This perspective article is a multi-voice effort to bring together different views and approaches, questions and insights, from researchers that work in this emerging area, the soft matter physics of the ground beneath our feet. In particular, we identify four major challenges concerned with the dynamics in and of the ground: (I) modeling from the grain scale, (II) near-criticality, (III) bridging scales, and (IV) life. For each challenge, we present a selection of topics by individual authors, providing specific context, recent advances, and open questions. Through this, we seek to provide an overview of the opportunities for the broad Soft Matter community to contribute to the fundamental understanding of the physics of the ground, strive towards a common language, and encourage new collaborations across the broad spectrum of scientists interested in the matter of the Earth's surface.

Tidewater-glacier response to supraglacial lake drainage.

The flow speed of the Greenland Ice Sheet changes dramatically in inland regions when surface meltwater drains to the bed. But ice-sheet discharge to the ocean is dominated by fast-flowing outlet glaciers, where the effect of increasing surface melt on annual discharge is unknown. Observations of a supraglacial lake drainage at Helheim Glacier, and a consequent velocity pulse propagating down-glacier, provide a natural experiment for assessing the impact of changes in injected meltwater, and allow us to interrogate the subglacial hydrological system. We find a highly efficient subglacial drainage system, such that summertime lake drainage has little net effect on ice discharge. Our results question the validity of common remote-sensing approaches for inferring subglacial conditions, knowledge of which is needed for improved projections of sea-level rise.

A first constraint on basal melt-water production of the Greenland ice sheet.

The Greenland ice sheet has been one of the largest sources of sea-level rise since the early 2000s. However, basal melt has not been included explicitly in assessments of ice-sheet mass loss so far. Here, we present the first estimate of the total and regional basal melt produced by the ice sheet and the recent change in basal melt through time. We find that the ice sheet's present basal melt production is 21.4 +4.4/-4.0 Gt per year, and that melt generated by basal friction is responsible for about half of this volume. We estimate that basal melting has increased by 2.9 ± 5.2 Gt during the first decade of the 2000s. As the Arctic warms, we anticipate that basal melt will continue to increase due to faster ice flow and more surface melting thus compounding current mass loss trends, enhancing solid ice discharge, and modifying fjord circulation.

Indentation into a plastic fluid layer.

We study the indentation of a rigid object into a layer of a cohesive or non-cohesive plastic material. Existing approaches to this problem using slip-line theory assume that the penetration depth is relatively small, employing perturbation theory about a flat surface. Here, we use two alternative approaches to account for large penetration depths, and for the consequent spreading and uplift of the surrounding material. For a viscoplastic fluid, which reduces to an ideal plastic under the limit of vanishing viscosity, we adopt a viscoplastic version of lubrication theory. For a Mohr-Coulomb material, we adopt an extension of slip-line theory between two parallel plates to account for arbitrary indenter shapes. We compare the theoretical predictions of penetration and spreading with experiments in which a flat plate, circular cylinder or sphere are indented into layers of Carbopol or glass spheres with successively higher loads. We find reasonable agreement between theory and experiment, though with some discrepancies that are discussed. There is a clear layer-depth dependence of the indentation and uplift for the viscoplastic material. For a cylinder indented into a Mohr-Coulomb material, there is a much weaker dependence on layer depth.

Wettability-Independent Droplet Transport by Bendotaxis.

We demonstrate "bendotaxis," a novel mechanism for droplet self-transport at small scales. A combination of bending and capillarity in a thin channel causes a pressure gradient that, in turn, results in the spontaneous movement of a liquid droplet. Surprisingly, the direction of this motion is always the same, regardless of the wettability of the channel. We use a combination of experiments at a macroscopic scale and a simple mathematical model to study this motion, focusing in particular on the timescale associated with the motion. We suggest that bendotaxis may be a useful means of transporting droplets in technological applications, e.g., in developing self-cleaning surfaces, and discuss the implications of our results for such applications.

Rolling resistance of shallow granular deformation.

Experiments are conducted to measure the resistance experienced by light cylinders rolling over flat beds of granular media. Sand and glass spheres are used for the beds. The trajectories of the rolling cylinders are determined through optical tracking, and velocity and acceleration data are inferred through fits to these trajectories. The rolling resistance is dominated by a velocity-independent component, but a velocity-dependent drag exceeding the expected strength of air drag is also observed. The results are compared to a theoretical model based on a cohesionless Mohr-Coulomb rheology for a granular medium in the presence of gravity. The model idealizes the flow pattern underneath the rolling cylinder as a plastically deforming zone in front of a rigidly rotating plug attached to the cylinder, as proposed previously for cylinders rolling on perfectly cohesive plastic media. The leading-order, rate-independent rolling resistance observed experimentally is well reproduced by the model predictions.

Capillary Imbibition into Converging Tubes: Beating Washburn's Law and the Optimal Imbibition of Liquids.

We consider the problem of capillary imbibition into an axisymmetric tube for which the tube radius decreases in the direction of increasing imbibition. For tubes with constant radius, imbibition is described by Washburn's law (referred to here as the BCLW law to recognize the contributions of Bell, Cameron, and Lucas that predate Washburn). We show that imbibition into tubes with a power-law relationship between the radius and axial position generally occurs more quickly than imbibition into a constant-radius tube. By a suitable choice of the shape exponent, it is possible to decrease the time taken for the liquid to imbibe from one position to another by a factor of 2 compared to the BCLW law. We then show that a further small decrease in the imbibition time may be obtained by using a tube consisting of a cylinder joined to a cone of 3 times the cylinder length. For a given inlet radius, this composite shape attains the minimum imbibition time possible. We confirm our theoretical results with experiments on the tips of micropipettes and discuss the possible significance of these results for the control of liquid motion in microfluidic devices.

Heterometallic 20-membered {Fe16Ln4} (Ln = Sm, Eu, Gd, Tb, Dy, Ho) metallo-ring aggregates.

The reaction of triethanolamine (teaH(3)) with [Fe(III)(3)O(O(2)CCH(3))(6)(H(2)O)(3)]Cl·6H(2)O and Ln(NO(3))(3)·6H(2)O in acetonitrile yields [Fe(16)Ln(4)(tea)(8)(teaH)(12)(µ-O(2)CCH(3))(8)](NO(3))(4)·16H(2)O·xMeCN (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); x = 10 or 11). These 20-membered metallo-ring complexes are the largest such single-stranded oxygen-bridged rings so far reported. The structure is stabilised by two of the acetate ligands, which form anti,anti-bridges across the centre of the ring, pinching the ring and giving it rigidity. The magnetic properties are dominated by the antiferromagnetic couplings between the Fe(III) centres. Although the Fe(2) and Fe(6) sub-chains within the ring are fully spin-compensated at low temperatures with S(subchain) = 0, coupling between the Gd(III) cations and the Fe(III) centres at the ends of the sub-chains (in 3) results in a pinning of the lanthanide spins. The (57)Fe Mössbauer spectra of 3 and 5 obtained at low temperatures are consistent with the presence of Fe(III) intracluster strong antiferromagnetic coupling. The applied field spectrum for 3 reveals no magnetic hyperfine interaction apart from that of the nucleus with the applied field, while the one for 5 is a superposition of three subspectra which show contributions from each of the peripheral as well as from the central iron sites.

Family of Mn(III)(2)Ln(2)(mu(4)-O) compounds: syntheses, structures, and magnetic properties.

An isostructural family of tetranuclear aggregates [Mn(III)(2)Ln(2)(O)(Piv)(2)(hep)(4)(NO(3))(4)].MeCN (where Ln = Y(III) (1), Pr(III) (2), Nd(III) (3), Gd(III) (4), Tb(III) (5), Dy(III) (6), Ho(III) (7), and Yb(III) (8)) is reported. They were obtained from the reactions of 2-(2-hydroxyethyl)pyridine (hepH) with a preformed hexanuclear manganese complex, [Mn(6)], and the respective lanthanide salt. The complexes are isomorphous and represent a new heterometallic 3d-4f complex type for this class of ligand. The structural core of 1-8 consists of a distorted Mn(2)Ln(2) tetrahedron with the four metal centers linking through a mu(4)-O(2-) bridging atom. The magnetic properties of all complexes were investigated by variable temperature magnetic susceptibility and magnetization measurements. The magnetic data of all compounds suggest that antiferromagnetic interactions are present between adjacent paramagnetic centers. Complexes 5-7 containing highly anisotropic lanthanide ions (Tb, Dy, and Ho) show slow relaxation of their magnetization.

Magnetic coordination clusters and networks: synthesis and topological description.

With the discovery of the phenomenon of single-molecule magnetism, coordination chemists have turned their attention to synthesizing cluster aggregates of paramagnetic ions. This has led to a plethora of coordination clusters with various topologies and diverse magnetic properties. In this paper, we present ways of describing and understanding such compounds as well as outlining a new approach, which we have recently developed, to describing cluster topology. Our approach is based upon and pays tribute to the huge contribution made to coordination chemistry through the development of the Schläfli symbols for describing architectures. To illustrate the developments that are taking place in modern coordination chemistry, we start with some basic definitions of relevance to what follows. Then we describe approaches to discovering new magnetically interesting 3d/4f clusters, assigning their topological descriptions. Finally, we show how the concepts behind the construction of metal-organic frameworks can be extended to using clusters as nodes in the frameworks to give super metal-organic frameworks.

Opening up a dysprosium triangle by ligand oximation.

A simple trinuclear dysprosium complex shows complex slow relaxation of the magnetisation.

Tridecanuclear [Mn(III)5Ln(III)8] complexes derived from N-(t)butyl-diethanolamine: synthesis, structures, and magnetic properties.

The synthesis, structures and magnetic properties of a family of heterometallic [Mn(III)(5)Ln(III)(8)(mu(3)-OH)(12)(L(2))(4)(piv)(12)(NO(3))(4)(OAc)(4)](-) (Ln = Pr, 2; Nd, 3; Sm, 4; Gd, 5; Tb, 6) aggregates are reported. The complexes were obtained from the direct reaction of N-(t)butyldiethanolamine (H(2)L(2)) with Mn(OAc)(2) x 4 H(2)O and Ln(NO(3))(3) x 6 H(2)O in the presence of pivalic acid (pivH) in MeCN under ambient conditions. Compounds 2-6 are isomorphous and crystallize in the monoclinic space group P2(1)/n with four molecules in the unit cell. The complexes have a centrosymmetric tridecanuclear anionic core consisting of two distorted inner heterometallic [Mn(III)Ln(III)(3)(mu(3)-OH)(4)](8+) cubane subunits sharing a common Mn vertex flanked by four edge-sharing heterometallic [Mn(III)Ln(III)(2)(mu(3)-OH)(4)](5+) defect cubane units. Complexes 2-6 are the first high-nuclearity 3d-4f aggregates reported to date using (t)Bu-deaH(2) as ligand. These compounds show no evidence of slow relaxation behavior above 1.8 K, which appears to be the consequence of the very weak or non-existent magnetic interactions between the Mn(III) and Ln(III) ions resulting from the particular angles at the bridging oxygens.

Synthesis of a metal-organic framework film by direct conversion technique for VOCs sensing.

For the first time, a metal-organic framework Zn(3)(BTC)(2) film has been successfully synthesized on the substrate of zinc wafer by a direct conversion technique. The obtained crystal densities and inter-growth of the film have been improved via the zinc wafer conversion method. The effect of synthesis conditions on the crystallization of Zn(3)(BTC)(2) and activation of the substrate were determined to optimize the strategies for the synthesis of continuous and stable layers. The crystallization took place by converting the activated zinc layer on the substrate. The reaction between the substrate-generated zinc source and the H(3)BTC clear solution yielded the best inter-growth of crystals and formed a high-density coating. More interestingly, the fluorescence emission of the Zn(3)(BTC)(2) film was found to be highly sensitive and selective sensing to dimethylamine among different VOCs. The fluorescence intensity decreased with increasing contents of dimethylamine in ethanol solution due to weak fluorescence quenching effect. This high-quality MOF film may find promising applications in sensors, especially in VOCs sensing.

A [Mn18Dy] SMM resulting from the targeted replacement of the central MnII in the S = 83/2 [Mn19]-aggregate with DyIII.

Anisotropy can be introduced into the [Mn(19)]-aggregate, which currently has the highest known spin ground state of S = 83/2, by the targeted replacement of the central Mn(II) cation with Dy(III) leading to a [Mn(18)Dy] complex with the same core topology showing slow relaxation of the magnetisation.

Di-, tetra- and hexanuclear iron(III), manganese(II/III) and copper(II) complexes of Schiff-base ligands derived from 6-substituted-2-formylphenols.

Acyclic Schiff base ligands, derived from the condensation of 2,3-disubstituted benzaldehydes and 1,3-diaminopropan-2-ol, react with iron(II/III), manganese(II/III) and copper(II) salts to give di-, tetra- and hexanuclear complexes [Fe(III)(2)(L5)(2)].2MeOH (), [Fe(III)(4)(mu(3)-OMe)(2)(HL4)(2)Cl(2)] (), [Mn(II)(2)Mn(III)(2)(micro-OMe)(2)(HL4)(2)(DMF)(2)].2DMF () and [Cu(II)(6)(L5)(2)(micro(5)-SO(4))(2)(micro-SO(4))(MeOH)(2)].H(2)O.15.5(MeOH).15.5(MeCN) (). All compounds have been characterised by X-ray crystallography. Variable-temperature solid-state dc magnetisation studies have been performed in the temperature range 1.8-300 K. Antiferromagnetic interactions are present in all the compounds. The dinuclear compound has a zero total spin ground state with J = -9.66(1) cm(-1) and g = 2.07(1). The magnetic data for the tetranuclear compounds and have been interpreted using a tetranuclear butterfly model (b = body, w = wingtip) with the parameters: J(wb) = -9.35(4) cm(-1), J(bb) = -6.02(7) cm(-1), zJ' = -0.21(4) cm(-1) and g = 2.03(1) for ; and J(wb) = -3.40(3) cm(-1), J(bb) = -8.11(7) cm(-1), zJ' = -0.042(2) cm(-1) and g = 2.0 (fixed) for . The hexanuclear compound contains two {Cu(3)(L5)(MeOH)} units linked by three sulfate ligands: antiferromagnetic interactions are present in each trinuclear unit leading to two S = 1/2 motifs which do not or only very weakly interact across the sulfate bridges.

Syntheses, structures and electronic properties of zwitterionic iron(II) and cobalt(II) complexes featuring ambidentate tris(pyrazolyl)methanide ligands.

By deprotonation of the corresponding tris(pyrazolyl)methane ((Me)Tpm) precursor complexes [M((Me)Tpm)(2)][(OTf)(2)] (1 and 2), the zwitterionic tris(pyrazolyl)methanide iron(II) (3) and cobalt(II) (4) "sandwich" complexes of the general formula [M((Me)Tpmd)(2)] are easily accessible. The structurally characterised complexes 3 and 4 are the first such homoleptic 3d transition metal species to feature two "naked", outward pointing pyramidal carbanions. Density functional theory calculations show metal-centred HOMOs and LUMOs with the destabilised carbanion orbitals in the energy region of the filled transition-metal-centred frontier orbitals. The electronic structures of these complexes have been investigated in detail by various spectroscopic techniques such as NMR, EPR, SQUID, Mössbauer, etc. Both complexes adopt a high-spin (HS) configuration at room temperature in solution and in the solid state. A thermally induced high-spin to low-spin (HS-LS) transition is observed for the iron(II) complex 3. The HS-LS transition temperature of 3 in solution differs from that in the solid state, which in turn strongly depends on the amount of solvent molecules in the crystal lattice. Electrochemical studies on the corresponding cobalt(II) complex 4 provide evidence for a HS-Co(II) <==> LS-Co(III) transition upon oxidation, which was confirmed by preliminary synthetic oxidation reactions. Overall, it can be concluded that the related kappa(3)N-donor ligands tris(pyrazolyl)hydroborates (Tp(R)) and (R)Tpmd ligands have similar bonding properties and that the metal cations experience more or less the same ligand environment.

"Twin copper source" growth of metal-organic framework membrane: Cu(3)(BTC)(2) with high permeability and selectivity for recycling H(2).

In this communication, the copper net supported Cu(3)(BTC)(2) membranes have been successfully synthesized by means of a "twin copper source" technique. Separation studies on gaseous mixtures (H(2)/CO(2), H(2)/CH(4), and H(2)/N(2)) using the membrane revealed that the membrane possesses high permeability and selectivity for H(2) over CO(2), N(2), and CH(4). Compared with the conventional zeolite membranes, the copper net supported Cu(3)(BTC)(2) membrane exhibited high permeation flux in gas separation. Such highly efficient copper net supported Cu(3)(BTC)(2) membranes could be used to separate, recycle, and reuse H(2) exhausted from steam reforming natural gas.

Spin chirality in a molecular dysprosium triangle: the archetype of the noncollinear ising model.

Single crystal magnetic studies combined with a theoretical analysis show that cancellation of the magnetic moments in the trinuclear Dy3+ cluster [Dy{3}(mu{3}-OH)2L3Cl(H2O){5}]Cl{3}, resulting in a nonmagnetic ground doublet, originates from the noncollinearity of the single-ion easy axes of magnetization of the Dy3+ ions that lie in the plane of the triangle at 120 degrees one from each other. This gives rise to a peculiar chiral nature of the ground nonmagnetic doublet and to slow relaxation of the magnetization with abrupt accelerations at the crossings of the discrete energy levels.

Heterometallic [Mn5-Ln4] single-molecule magnets with high anisotropy barriers.

The reaction of [Mn6O2(Piv)(10)(4-Me-py)(2.5)(PivH)(1.5)] (1) (py: pyridine, Piv: pivilate) with N-methyldiethanolamine (mdeaH2) and Ln(NO3)3 x 6 H2O in MeCN leads to a series of nonanuclear compounds [Mn5Ln4(O)6(mdea)2(mdeaH)2(Piv)6(NO3)4(H2O)2]2 MeCN (Ln=Tb(III) (2), Dy(III) (3), Ho(III) (4), Y(III) (5)). Single-crystal X-ray diffraction shows that compounds 2-5 are isostructural, with the central core composed of two distorted {Mn(IV)Mn(III)Ln2O4} cubanes sharing a Mn(IV) vertex, representing a new heterometallic 3d-4f motif for this class of ligand. The four new compounds display single-molecule magnet (SMM) behaviour, which is modulated by the lanthanide ion used. Moreover, the values found for Delta(eff) and tau(o) for 3 of 38.6 K and 3.0 x 10(-9) s respectively reveal that the complex 3 exhibits the highest energy barrier recorded so far for 3d-4f SMMs. The slow relaxation of the magnetisation for 3 was confirmed by mu-SQUID measurements on an oriented single crystal and the observation of M versus H hysteresis loops below 1.9 K.