Cement-rock interaction : infiltration of a high-pH solution into a fractured granite core

Within the framework of the HPF project (Hyperalkaline Plume in Fractured Rock) at the Grimsel Test Site (Switzerland), a small scale core infiltration experiment was performed at the University of Bern. A high-pH solution was continuously injected, under a constant pressure gradient, into a cylindrical core of granite containing a fracture. This high-pH solution was a synthetic version of solutions characteristic of early stages in the degradation of cement. The interaction between the rock and the solutions was reflected by significant changes in the composition of the injected solution, despite the negligible pH-buffering capacity, and a decrease in the permeability of the rock. Changes in the mineralogy and porosity of the fault gouge filling the fracture were only minor. Within the new LCS (Long-Term Cement Studies) project at Grimsel, new one-dimensional reactive transport modeling using CrunchFlow has been used to improve the interpretation of the experimental results. Dispersive and advective solute transport, adsorption processes and mineral reaction kinetics have been taken into account. The evolution of solution composition is mainly controlled by dissolution/precipitation reactions. Adsorption processes (cation exchange, surface complexation) only play a role in the very early stages of the experiment

Bifurcations in the Lozi map

We study the presence in the Lozi map of a type of abrupt order-to-order and order-to-chaos transitions which are mediated by an attractor made of a continuum of neutrally stable limit cycles, all with the same period.Comment: 17 pages, 12 figure

Heavy-to-light scalar form factors from Muskhelishvili-Omn\`es dispersion relations

By solving the Muskhelishvili-Omn\`es integral equations, the scalar form factors of the semileptonic heavy meson decays $D\to\pi \bar \ell \nu_\ell$, $D\to \bar{K} \bar \ell \nu_\ell$, $\bar{B}\to \pi \ell \bar\nu_\ell$ and $\bar{B}_s\to K \ell \bar\nu_\ell$ are simultaneously studied. As input, we employ unitarized heavy meson-Goldstone boson chiral coupled-channel amplitudes for the energy regions not far from thresholds, while, at high energies, adequate asymptotic conditions are imposed. The scalar form factors are expressed in terms of Omn\`es matrices multiplied by vector polynomials, which contain some undetermined dispersive subtraction constants. We make use of heavy quark and chiral symmetries to constrain these constants, which are fitted to lattice QCD results both in the charm and the bottom sectors, and in this latter sector to the light-cone sum rule predictions close to $q^2=0$ as well. We find a good simultaneous description of the scalar form factors for the four semileptonic decay reactions. From this combined fit, and taking advantage that scalar and vector form factors are equal at $q^2=0$, we obtain $|V_{cd}|=0.244\pm 0.022$, $|V_{cs}|=0.945\pm 0.041$ and $|V_{ub}|=(4.3\pm 0.7)\times10^{-3}$ for the involved Cabibbo-Kobayashi-Maskawa (CKM) matrix elements. In addition, we predict the following vector form factors at $q^2=0$: $|f_+^{D\to\eta}(0)|=0.01\pm 0.05$, $|f_+^{D_s\to K}(0)|=0.50 \pm 0.08$, $|f_+^{D_s\to\eta}(0)|=0.73\pm 0.03$ and $|f_+^{\bar{B}\to\eta}(0)|=0.82 \pm 0.08$, which might serve as alternatives to determine the CKM elements when experimental measurements of the corresponding differential decay rates become available. Finally, we predict the different form factors above the $q^2-$regions accessible in the semileptonic decays, up to moderate energies amenable to be described using the unitarized coupled-channel chiral approach.Comment: includes further discussions and references; matches the accepted versio

Accuracy control in ultra-large-scale electronic structure calculation

Numerical aspects are investigated in ultra-large-scale electronic structure calculation. Accuracy control methods in process (molecular-dynamics) calculation are focused. Flexible control methods are proposed so as to control variational freedoms, automatically at each time step, within the framework of generalized Wannier state theory. The method is demonstrated in silicon cleavage simulation with 10^2-10^5 atoms. The idea is of general importance among process calculations and is also used in Krylov subspace theory, another large-scale-calculation theory.Comment: 8 pages, 3 figures. To appear in J.Phys. Condens. Matter. A preprint PDF file in better graphics is available at http://fujimac.t.u-tokyo.ac.jp/lses/index_e.htm

Ordering dynamics of blue phases entails kinetic stabilization of amorphous networks

The cubic blue phases of liquid crystals are fascinating and technologically promising examples of hierarchically structured soft materials, comprising ordered networks of defect lines (disclinations) within a liquid crystalline matrix. We present the first large-scale simulations of their domain growth, starting from a blue phase nucleus within a supercooled isotropic or cholesteric background. The nucleated phase is thermodynamically stable; one expects its slow orderly growth, creating a bulk cubic. Instead, we find that the strong propensity to form disclinations drives the rapid disorderly growth of a metastable amorphous defect network. During this process the original nucleus is destroyed; re-emergence of the stable phase may therefore require a second nucleation step. Our findings suggest that blue phases exhibit hierarchical behavior in their ordering dynamics, to match that in their structure.Comment: 11 pages, 5 figures, 2 supplementary figures, 2 supplementary tables, accepted by PNA

Systematically improvable optimized atomic basis sets for {\it ab inito} calculations

We propose a unique scheme to construct fully optimized atomic basis sets for density-functional calculations. The shapes of the radial functions are optimized by minimizing the {\it spillage} of the wave functions between the atomic orbital calculations and the converged plane wave calculations for dimer systems. The quality of the bases can be systematically improved by increasing the size of the bases within the same framework. The scheme is easy to implement and very flexible. We have done extensive tests of this scheme for wide variety of systems. The results show that the obtained atomic basis sets are very satisfactory for both accuracy and transferability

Large-scale electronic structure theory for simulating nanostructure process

Fundamental theories and practical methods for large-scale electronic structure calculations are given, in which the computational cost is proportional to the system size. Accuracy controlling methods for microscopic freedoms are focused on two practical solver methods, Krylov-subspace method and generalized-Wannier-state method. A general theory called the 'multi-solver' scheme is also formulated, as a hybrid between different solver methods. Practical examples are carried out in several insulating and metallic systems with 10^3-10^5 atoms. All the theories provide general guiding principles of constructing an optimal calculation for simulating nanostructure processes, since a nanostructured system consists of several competitive regions, such as bulk and surface regions, and the simulation is designed to reproduce the competition with an optimal computational cost.Comment: 19 pages, 6 figures. To appear in J. Phys. Cond. Matt. A preprint PDF file in better graphics is available at http://fujimac.t.u-tokyo.ac.jp/lses/index_e.htm

Theoretical analysis of magnetic coupling in sandwich clusters V_n(C_6H_6)_{n+1}

The mechanism of ferromagnetism stability in sandwich clusters V$_n$(C$_6$H$_6$)$_{n+1}$ has been studied by first-principles calculation and model analysis. It is found that each of the three types of bonds between V and benzene (Bz) plays different roles. V 3d$_{z^2}$ orbital, extending along the molecular axis, is weakly hybridized with Bz's HOMO-1 orbital to form the $\sigma$-bond. It is quite localized and singly occupied, which contributes 1$\mu_B$ to the magnetic moment but little to the magnetic coupling of neighboring V magnetic moments. The in-plane d$_{x^2-y^2}$, d$_{xy}$ orbitals are hybridized with the LUMO of Bz and constitute the $\delta$-bond. This hybridization is medium and crucial to the magnetic coupling though the $\delta$ states have no net contribution to the total magnetic moment. d$_{xz}$, d$_{yz}$ and HOMO of Bz form a quite strong $\pi$-bond to hold the molecular structure but they are inactive in magnetism because their energy levels are far away from the Fermi level. Based on the results of first-principles calculation, we point out that the ferromagnetism stability is closely related with the mechanism proposed by Kanamori and Terakura [J. Kanamori and K. Terakura, J. Phys. Soc. Jpn. 70, 1433 (2001)]. However, the presence of edge Bz's in the cluster introduces an important modification. A simple model is constructed to explain the essence of the physical picture.Comment: 16 pages, 7 figure