Theory of Nucleation in Phase-separating Nanoparticles

The basic physics of nucleation in solid \hl{single-crystal} nanoparticles is revealed by a phase-field theory that includes surface energy, chemical reactions and coherency strain. In contrast to binary fluids, which form arbitrary contact angles at surfaces, complete "wetting" by one phase is favored at binary solid surfaces. Nucleation occurs when surface wetting becomes unstable, as the chemical energy gain (scaling with area) overcomes the elastic energy penalty (scaling with volume). The nucleation barrier thus decreases with the area-to-volume ratio and vanishes below a critical size, and nanoparticles tend to transform in order of increasing size, leaving the smallest particles homogeneous (in the phase of lowest surface energy). The model is used to simulate phase separation in realistic nanoparticle geometries for \ce{Li_XFePO4}, a popular cathode material for Li-ion batteries, and collapses disparate experimental data for the nucleation barrier, with no adjustable parameters. Beyond energy storage, the theory generally shows how to tailor the elastic and surface properties of a solid nanostructure to achieve desired phase behavior.Comment: 7 pages, 4 fig

Coherency strain and the kinetics of phase separation in LiFePO4

A theoretical investigation of the effects of elastic coherency on the thermodynamics, kinetics, and morphology of intercalation in single LiFePO4 nanoparticles yields new insights into this important battery material. Anisotropic elastic stiffness and misfit strains lead to the unexpected prediction that low-energy phase boundaries occur along {101} planes, while conflicting reports of phase boundary orientations are resolved by a partial loss of coherency in the {100} direction. Elastic relaxation near surfaces leads to the formation of a striped morphology, whose characteristic length scale is predicted by the model and yields an estimate of the interfacial energy. The effects of coherency strain on solubility and galvanostatic discharge are studied with a reaction-limited phase-field model, which quantitatively captures the influence of misfit strain, particle size, and temperature on solubility seen in experiments. Coherency strain strongly suppresses phase separation during discharge, which enhances rate capability and extends cycle life. The effects of elevated temperature and the feasibility of nucleation are considered in the context of multi-particle cathodes

Flexible synthesis of polyfunctionalised 3-fluoropyrroles

An efficient and selective approach for the synthesis of polyfunctionalised 3-fluoropyrroles has been developed starting from commercial aldehydes. The methodology is concise, efficient and allows for the modular and systematic assembly of polysubstituted 3-fluoropyrroles. This synthesis provides an alternative and highly convergent strategy for the generation of these chemically and biologically important units

Implications of nonzero θ13\theta_{13} for the neutrino mass hierarchy

The Daya Bay, RENO, and Double Chooz experiments have discovered a large non-zero value for $\theta_{13}$. We present a global analysis that includes these three experiments, Chooz, the Super-K atmospheric data, and the $\nu_\mu \rightarrow \nu_e$ T2K and MINOS experiments that are sensitive to the hierarchy and the sign of $\theta_{13}$. We report preliminary results in which we fix the mixing parameters other than $\theta_{13}$ to those from a recent global analysis. Given there is no evidence for a non-zero CP violation, we assume $\delta=0$. T2K and MINOS lie in a region of $L/E$ where there is a hierarchy degeneracy in the limit of $\theta_{13}\rightarrow 0$ and no matter interaction. For non-zero $\theta_{13}$, the symmetry is partially broken, but a degeneracy under the simultaneous exchange of both hierarchy and the sign of $\theta_{13}$ remains. Matter effects break this symmetry such that the positions of the peaks in the oscillation probabilities maintain the two-fold symmetry, while the magnitude of the oscillations is sensitive to the hierarchy. This renders T2K and NO$\nu$A, with different baselines and different matter effects, better able in combination to distinguish the hierarchy and the sign of $\theta_{13}$. The large value of $\theta_{13}$ yields effects from atmospheric data that distinguish hierarchies. We find for normal hierarchy, positive $\theta_{13}$, $\sin^22\theta_{13}=0.090\pm0.020$ and is 0.2% probable it is the correct combination; for normal hierarchy, negative $\theta_{13}$, $\sin^22\theta_{13}=0.108\pm0.023$ and is 2.2% probable; for inverse hierarchy, positive $\theta_{13}$, $\sin^22\theta_{13}=0.110\pm0.022$ and is 7.1% probable; for inverse hierarchy, negative $\theta_{13}$, $\sin^22\theta_{13}=0.113\pm0.022$ and is 90.5% probable, results that are inconsistent with two similar analyses.Comment: 8 pages, 8 figures, to appear in Horizons of Innovative Theories, Experiments, and Supercomputing in Nuclear Physics (New Orleans, June 4-6, 2012