The effect of anisotropic elasticity on the yielding characteristics of overconsolidated natural clay

Quantitative application of elastoplastic theory to the yielding behaviour of natural soils has always been uncertain. Part of the reason is that the theory was developed for reconstituted materials with isotropic structure, in contrast to natural soils that are usually anisotropic. The approach considered in this study assumes that pre-yielding behaviour is governed by the theory of linear anisotropic elasticity and that yield loci in the mean effective stress ( p') – deviator stress (q) plane are aligned approximately along the coefficient of earth pressure (K0) line. The assumption of a rotated yield locus associated with anisotropic elastic behaviour within the state boundary surface indicates that the elastic wall within the state boundary surface is inclined. The form of the state boundary surface has been determined mathematically in terms of anisotropic elastic and Cam-Clay soil parameters. Stress path tests were conducted on samples of Belfast Upper Boulder Clay removed from a depth of 28 m below ground surface. Good agreement was found between predicted and measured yield loci. The study also examined the influence of subsequent isotropic compression on the yielding characteristics of the natural clay. The indications are that the anisotropy developed during deposition disappears when the sample is loaded to a stress level at least twice the stress generated during the original deposition process. The methods developed in the paper have also been applied to test results reported previously on Winnipeg clay, and good agreement was obtained.

Determining the electronic structure and chemical potentials of molecules in solution

A simulation scheme is proposed for determining the excess chemical potential of a substance in solution. First, a Monte Carlo simulation is performed with classical models for solute and solvent molecules. A representative sample of these configurations is then used in a hybrid quantum/classical (QM/MM) calculation, where the solute is treated quantum-mechanically, and the average electronic structure is used to construct an improved classical model. This procedure is iterated to self-consistency in the classical model, which in practice is attained in one or two steps, depending on the quality of the initial guess. The excess free energy of the molecule within the QM/MM approach is determined relative to the classical model using thermodynamic perturbation theory with a cumulant expansion. The procedure provides a method of constructing classical point charge models appropriate for the solution and gives a measure of the importance of solvent fluctuations.

Concertedness and solvent effects in multiple proton transfer reactions: The formic acid dimer in solution

The issue of multiple proton transfer (PT) reactions in solution is addressed by performing molecular dynamics simulations for a formic acid dimer embedded in a water cluster. The reactant species is treated quantum mechanically, within a density functional approach, while the solvent is represented by a classical model. By constraining different distances within the dimer we analyze the PT process in a variety of situations representative of more complex environments. Free energy profiles are presented, and analyzed in terms of typical solvated configurations extracted from the simulations. A decrease in the PT barrier height upon solvation is rationalized in terms of a transition state which is more polarized than the stable states. The dynamics of the double PT process is studied in a low-barrier case and correlated with solvent polarization fluctuations. Cooperative effects in the motion of the two protons are observed in two different situations: when the solvent polarization does not favor the transfer of one of the two protons and when the motion of the two protons is not synchronized. This body of observations is correlated with local structural and dynamical properties of the solvent in the vicinity of the reactant. (C) 2000 American Institute of Physics. [S0021-9606(00)51121-0].