Diffusive shielding stabilizes bulk nanobubble clusters

Using molecular dynamics, we study the nucleation and stability of bulk nanobubble clusters. We study the formation, growth, and final size of bulk nanobubbles. We find that, as long as the bubble-bubble interspacing is small enough, bulk nanobubbles are stable against dissolution. Simple diffusion calculations provide an excellent match with the simulation results, giving insight into the reason for the stability: nanobubbles in a cluster of bulk nanobubbles "protect" each other from diffusion by a shielding effect

On the friction coefficient of straight-chain aggregates

A methodology to calculate the friction coefficient of an aggregate in the continuum regime is proposed. The friction coefficient and the monomer shielding factors, aggregate-average or individual, are related to the molecule-aggregate collision rate that is obtained from the molecular diffusion equation with an absorbing boundary condition on the aggregate surface. Calculated friction coefficients of straight chains are in very good agreement with previous results, suggesting that the friction coefficients may be accurately calculated from the product of the collision rate and an average momentum transfer,the latter being independent of aggregate morphology. Langevin-dynamics simulations show that the diffusive motion of straight-chain aggregates may be described either by a monomer-dependent or an aggregate-average random force, if the shielding factors are appropriately chosen.Comment: 22 pages, 6 figures, revised version. To appear in the Journal of Colloid and Interface Scienc

Dynamics of Quasi-ordered Structure in a Regio-regulated pi-Conjugated Polymer:Poly(4-methylthiazole-2,5-diyl)

Dynamics of regio-regulated Poly(4-methylthiazole-2,5-diyl) [HH-P4MeTz] was inves tigated by solid-state 1H, 2D, 13C NMR spectroscopies, and differential scanning calorimetry(DSC) measurements. DSC, 2D quadrupolar echo NMR, 13C cross-polarization and magic-angle spinning(CPMAS) NMR, and 2D spin-echo(2DSE) CPMAS NMR spectroscopy suggest existence of a quasi-ordered phase in which backbone twists take place with weakened pi-stackings. Two-dimensional exchange 2D NMR(2DEX) detected slow dynamics with a rate of an order of 10^2Hz for the CD_3 group in d_3-HH-P4MeTz at 288K. The frequency dependence of proton longitudinal relaxation rate at 288K shows a omega^-1/2 dependence, which is due to the one-dimensional diffusion-like motion of backbone conformational modulation waves. The diffusion rate was estimated as 3+/-2 GHz, which was approximately 10^7 times larger than that estimated by 2DEX NMR measurements. These results suggest that there exists anomalous dispersion of modulation waves in HH-P4MeTz. The one-dimensional group velocity of the wave packet is responsible for the behavior of proton longitudinal relaxation time. On the other hand, the 2DEX NMR is sensitive to phase velocity of the nutation of methyl groups that is associated with backbone twists. From proton T_1 and T_2 measurements, the activation energy was estimated as 2.9 and 3.4 kcal/mol, respectively. These were in agreement with 3.0 kcal/mol determined by Moller-Plesset(MP2) molecular orbital(MO) calculation. We also performed chemical shielding calculation of the methyl-carbon in order to understand chemical shift tensor behavior, leading to the fact that a quasi-ordered phase coexist with the crystalline phase.Comment: 14 pages, 11 figures, to appear in Phys.Rev.

Control of heat flux using computationally designed metamaterials

To gain control over the diffusive heat flux in a given domain, one has to design metamaterials with a specifc distribution of the generally anisotropic thermal conductivity throughout the domain. Until now, the appropriate conductivity distribution was usually determined using transformation thermodynamics. By this way, only a few particular cases of heat flux control in simple domains having simple boundary conditions were studied. As a more general approach, we propose to define the heat control problem as an optimization problem where we minimize the error in guiding the heat flux in a given way, taking as design variables the parameters that define the variable microstructure of the metamaterial. Anisotropic conductivity is introduced by using a metamaterial made of layers of two materials with highly dfferent conductivities, the thickness of the layers and their orientation throughout the domain are the current design variables. As an application example we design a device that thermally shields the region it encloses, while it keeps unchanged the flux outside it.Preprin

Hydrogen Motion in Magnesium Hydride by NMR

In coarse-grained MgH2, the diffusive motion of hydrogen remains too slow (<10^5 hops s^−1) to narrow the H NMR line up to 400 °C. Slow-motion dipolar relaxation time T1D measurements reveal the motion, with hopping rate ωH from 0.1 to 430 s^−1 over the range of 260 to 400 °C, the first direct measurement of H hopping in MgH2. The ωH data are described by an activation energy of 1.72 eV (166 kJ/mol) and attempt frequency of 2.5 × 10^15 s^−1. In ball-milled MgH2 with 0.5 mol % added Nb2O5 catalyst, line-narrowing is evident already at 50 °C. The line shape shows distinct broad and narrow components corresponding to immobile and mobile H, respectively. The fraction of mobile H grows continuously with temperature, reaching ∼30% at 400 °C. This demonstrates that this material’s superior reaction kinetics are due to an increased rate of H motion, in addition to the shorter diffusion paths from ball-milling. In ball-milled MgH2 without additives, the line-narrowed component is weaker and is due, at least in part, to trapped H2 gas. The spin−lattice relaxation rates T1^−1 of all materials are compared, with ball-milling markedly increasing T1^−1. The weak temperature dependence of T1^−1 suggests a mechanism with paramagnetic relaxation centers arising from the mechanical milling

Oxygen transport across the benthic boundary layer: from a 1-D to a 3-D view

The sediment-water interface is a fascinating environment.Bordering the dynamic processes between hydrosphere andgeosphere, it is the gate-keeper for the benthic-pelagiccoupling of carbon and nutrient cycles in aquatic ecosystems.In this region boundary layer hydrodynamics interact withtransport processes across the interface, organic matterdeposited on the sediment surface supports and focuses thebiological activity to a thin veneer teeming with life, and steepchemical gradients provide diverse zones for biological andgeochemical processes.Just as the earth surface appears flat when viewed fromorbit, the sediment surface appears flat when we read mostbiogeochemical literature which describes it with only avertical axis. However, many aspects of sediment biology andgeochemistry require a three-dimensional view to understandtheir essential properties. We need novel approaches withgreater information capacity to study the spatial structures ofbiota, environments, and processes. To stimulate thedevelopment of such approaches, this short review will discuss some of the small-scale characteristics of the benthic boundarylayer, and illustrates the 3-D world of the sea floor based onrecent progress in analytical and experimental techniques. Thefew examples used are taken mostly from the work of our owngroup since brevity forces us to neglect the excellent work ofmany colleagues

Theory of diffusion-influenced reactions in complex geometries

Chemical reactions involving diffusion of reactants and subsequent chemical fixation steps are generally termed "diffusion-influenced" (DI). Virtually all biochemical processes in living media can be counted among them, together with those occurring in an ever-growing number of emerging nano-technologies. The role of the environment's geometry (obstacles, compartmentalization) and distributed reactivity (competitive reactants, traps) is key in modulating the rate constants of DI reactions, and is therefore a prime design parameter. Yet, it is a formidable challenge to build a comprehensive theory able to describe the environment's "reactive geometry". Here we show that such a theory can be built by unfolding this many-body problem through addition theorems for special functions. Our method is powerful and general and allows one to study a given DI reaction occurring in arbitrary "reactive landscapes", made of multiple spherical boundaries of given size and reactivity. Importantly, ready-to-use analytical formulas can be derived easily in most cases.Comment: 5 pages, 3 figure

Zero-bias anomaly in disordered wires

We calculate the low-energy tunneling density of states $\nu(\epsilon, T)$ of an $N$-channel disordered wire, taking into account the electron-electron interaction non-perturbatively. The finite scattering rate $1/\tau$ results in a crossover from the Luttinger liquid behavior at higher energies, $\nu\propto\epsilon^\alpha$, to the exponential dependence $\nu (\epsilon, T=0)\propto \exp{(-\epsilon^*/\epsilon)}$ at low energies, where $\epsilon^*\propto 1/(N \tau)$. At finite temperature $T$, the tunneling density of states depends on the energy through the dimensionless variable $\epsilon/\sqrt{\epsilon^* T}$. At the Fermi level $\nu(\epsilon=0,T) \propto \exp (-\sqrt{\epsilon^*/T})$.Comment: 5 pages, 1 figur