Éamonn Murray

We propose a second version of the van der Waals density functional of Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)], employing a more accurate semilocal exchange functional and the use of a large-$N$ asymptote gradient correction in determining the vdW kernel. The predicted binding energy, equilibrium separation, and potential-energy curve shape are close to those of accurate quantum chemical calculations on 22 duplexes. We anticipate the enabling of chemically accurate calculations in sparse materials of importance for condensed matter, surface, chemical, and biological physics.

Sparse matter is abundant and has both strong local bonds and weak nonbonding forces, in particular nonlocal van der Waals (vdW) forces between atoms separated by empty space. It encompasses a broad spectrum of systems, like soft matter, adsorption systems and biostructures. Density-functional theory (DFT), long since proven successful for dense matter, seems now to have come to a point, where useful extensions to sparse matter are available. In particular, a functional form, vdW-DF (Dion et al 2004 Phys. Rev. Lett. 92 246401; Thonhauser et al 2007 Phys. Rev. B 76 125112), has been proposed for the nonlocal correlations between electrons and applied to various relevant molecules and materials, including to those layered systems like graphite, boron nitride and molybdenum sulfide, to dimers of benzene, polycyclic aromatic hydrocarbons (PAHs), doped benzene, cytosine and DNA base pairs, to nonbonding forces in molecules, to adsorbed molecules, like benzene, naphthalene, phenol and adenine on graphite, alumina and metals, to polymer and carbon nanotube (CNT) crystals, and hydrogen storage in graphite and metal-organic frameworks (MOFs), and to the structure of DNA and of DNA with intercalators. Comparison with results from wavefunction calculations for the smaller systems and with experimental data for the extended ones show the vdW-DF path to be promising. This could have great ramifications.

Intense femtosecond laser excitation can produce transient states of matter that would otherwise be inaccessible to laboratory investigation. At high excitation densities, the interatomic forces that bind solids and determine many of their properties can be substantially altered. Here, we present the detailed mapping of the carrier density-dependent interatomic potential of bismuth approaching a solid-solid phase transition. Our experiments combine stroboscopic techniques that use a high-brightness linear electron accelerator-based x-ray source with pulse-by-pulse timing reconstruction for femtosecond resolution, allowing quantitative characterization of the interatomic potential energy surface of the highly excited solid.

We present a comparison of exchange-only interaction energies obtained using several standard exchange functionals in the generalized gradient approximation to Hartree-Fock results for interacting molecules. We observe that functionals with an enhancement factor using a 2/5 power dependence on the gradient of the density for large density gradients offer consistently better agreement with Hartree-Fock calculations than that of alternative functionals. We revisit the functional offering the closest agreement and recalculate it to include its exact large gradient dependence.

Composites of graphene in a chitosan-lactic acid matrix were prepared to create conductive hydrogels that are processable, exhibit tunable swelling properties and show excellent biocompatibility. The addition of graphene to the polymer matrix also resulted in significant improvements to the mechanical strength of the hydrogels, with the addition of just 3 wt% graphene resulting in tensile strengths increasing by over 200%. The composites could be easily processed into three-dimensional scaffolds with finely controlled dimensions using additive fabrication techniques and fibroblast cells demonstrate good adhesion and growth on their surfaces. These chitosan-graphene composites show great promise for use as conducting substrates for the growth of electro-responsive cells in tissue engineering.