Publications

Memristors were proposed in the early 1970s by Leon Chua as a new electrical element linking charge to flux. Since that first introduction, these devices have positioned themselves to be considered as possible fundamental ones for the generations of electronic devices to come. In this paper, we propose a new way to investigate the effects of the electrical variables on the memristance of a device, and we successfully apply this technique to model the behavior of a TiN/Ti/HfO2/W ReRAM structure. To do so, we initially apply the Dynamic Route Map technique in the general case to obtain an approximation to the differential equation that determines the behaviour of the device. This is performed by choosing a variable of interest and observing the evolution of its own temporal derivative versus both its value and the applied voltage. Then, according to this technique, it is possible to obtain an approach to the governing equations with no need to make any assumption about the underlying physical mechanisms, by fitting a function to this. We have used a polynomial function, which allows accurate reproduction of the observed electrical behavior of the measured devices, by integrating the resulting differential equation system.

Advances in solid-state batteries have primarily been driven by the discovery of superionic conducting structural frameworks that function as solid electrolytes. We demonstrate the ability of high-entropy metal cation mixes to improve ionic conductivity in a compound, which leads to less reliance on specific chemistries and enhanced synthesizability. The local distortions introduced into high-entropy materials give rise to an overlapping distribution of site energies for the alkali ions so that they can percolate with low activation energy. Experiments verify that high entropy leads to orders-of-magnitude higher ionic conductivities in lithium (Li)–sodium (Na) superionic conductor (Li-NASICON), sodium NASICON (Na-NASICON), and Li-garnet structures, even at fixed alkali content. We provide insight into selecting the optimal distortion and designing high-entropy superionic conductors across the vast compositional space.

We report observations from HST of Cepheids in the hosts of 42 SNe Ia used to calibrate the Hubble constant (H0). These include all suitable SNe Ia in the last 40 years at z<0.01, measured with >1000 orbits, more than doubling the sample whose size limits the precision of H0. The Cepheids are calibrated geometrically from Gaia EDR3 parallaxes, masers in N4258 (here tripling that Cepheid sample), and DEBs in the LMC. The Cepheids were measured with the same WFC3 instrument and filters (F555W, F814W, F160W) to negate zeropoint errors. We present multiple verifications of Cepheid photometry and tests of background determinations that show measurements are accurate in the presence of crowding. The SNe calibrate the mag-z relation from the new Pantheon+ compilation, accounting here for covariance between all SN data, with host properties and SN surveys matched to negate differences. We decrease the uncertainty in H0 to 1 km/s/Mpc with systematics. We present a comprehensive set of ~70 analysis variants to explore the sensitivity of H0 to selections of anchors, SN surveys, z range, variations in the analysis of dust, metallicity, form of the P-L relation, SN color, flows, sample bifurcations, and simultaneous measurement of H(z). Our baseline result from the Cepheid-SN sample is H0=73.04+-1.04 km/s/Mpc, which includes systematics and lies near the median of all analysis variants. We demonstrate consistency with measures from HST of the TRGB between SN hosts and NGC 4258 with Cepheids and together these yield 72.53+-0.99. Including high-z SN Ia we find H0=73.30+-1.04 with q0=-0.51+-0.024. We find a 5-sigma difference with H0 predicted by Planck+LCDM, with no indication this arises from measurement errors or analysis variations considered to date. The source of this now long-standing discrepancy between direct and cosmological routes to determining the Hubble constant remains unknown.

Versatile methods for iridium-catalyzed, kinetic asymmetric substitution of racemic, branched allylic esters are reported. These reactions occur with a variety of aliphatic, aryl, and heteroaryl allylic benzoates to form the corresponding allylic substitution products in high yields (74-96%) with good to excellent enantioselectivity (84-98% ee) with a scope that encompasses a range of anionic carbon and heteroatom nucleophiles. These kinetic asymmetric processes occur with distinct stereochemical courses for racemic aliphatic and aromatic allylic benzoates, and the high reactivity of branched allylic benzoates enables enantioselective allylic substitutions that are slow or poorly selective with linear allylic electrophiles.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The COBRA protein is found only in higher plants and algae, and has been implicated in cellulose synthesis, but its specific function remains unknown. To shed light on COBRA function we tested the ability of putative Arabidopsis COBRA orthologs to complement mutations in the COBRA gene. We expanded the previously published phylogenetic analysis and found that COBRA genes can be grouped into five clades. Representative COBRA genes from the different clades were expressed in a cobra mutant background. Surprisingly, none of the COBRA-LIKE genes was able to complement cobra, including the closest homolog which we found to bind cellulose with the same avidity as COBRA. We hypothesize that the lack of ability of the COBRA-LIKE genes to complement the cobra mutant is due to an unidentified binding interaction that is sensitive to the structure of the COBRA-LIKE proteins. However, membrane-based yeast two hybrid assays failed to identify positive interactors for COBRA.

Despite several reports on the surface phase transformations from a layered to a disordered spinel and a rock-salt structure at the surface of the Ni-rich cathodes, the precise structures and compositions of these surface phases are unknown. The phenomenon, in itself, is complex and involves the participation of several contributing factors. Of these factors, transition metal (TM) ion migration toward the interior of the particle and hence formation of TM-densified surface layers, triggered by oxygen loss, is thermodynamically probable. Here, we simulate the thermodynamic phase equilibria as a function of TM ion content in the cathode material in the context of lithium nickel oxides, using a combined approach of first-principles density functional calculations, the cluster expansion method, and grand canonical Monte Carlo simulations. We developed a unified lattice Hamiltonian that accommodates not only rock-salt like structures but also topologically different spinel-like structures. Also, our model provides a foundation to investigate metastable cation compositions and kinetics of the phase transformations. Our investigations predict the existence of several Ni-rich phases that were, to date, unknown in the scientific literature. Our simulated phase diagrams at finite temperature show a very low solubility range of the prototype spinel phase. We find a partially disordered spinel-like phase with far greater solubility that is expected to show very different Li diffusivity compared to that of the prototype spinel structure.