Time-Dependent Density-Functional Theory for Modeling Solid-State Fluorescence Emission of Organic Multicomponent Crystals.

We describe the approach for modeling solid-state fluorescence spectra of organic crystalline materials, using the recent implementation of time-dependent density-functional theory within the plane-wave/pseudopotential code CASTEP. The method accuracy is evaluated on a series of organic cocrystals displaying a range of emission wavelengths. In all cases the calculated spectra are in good to excellent agreement with experiment. The ability to precisely model the emission spectra offers novel insight into the role of intermolecular interactions and crystal packing on solid-state luminescence of organic chromophores, allowing the possibility of in silico design of organic luminescent materials.

Mechanism of enhancement of ferroelectricity of croconic acid with temperature.

A detailed study of the thermal behaviour of atomic motions in the organic ferroelectric croconic acid is presented in the temperature range 5-300 K. Using high-resolution inelastic neutron scattering and first-principles electronic-structure calculations within the framework of density functional theory and a quasiharmonic phonon description of the material, we find that the frequencies of the well defined doublet in inelastic neutron scattering spectra associated with out-of-plane motions of hydrogen-bonded protons decrease monotonically with temperature indicating weakening of these bonding motifs and enhancement of proton motions. Theoretical mean-square displacements for these proton motions are within 5% of experimental values. A detailed analysis of this observable shows that it is unlikely that there is a facile proton transfer along the direction of ferroelectric polarization in the absence of an applied electric field. Calculations predict constrained thermal motion of proton along crystallographic lattice direction c retaining the hydrogen bond motif of the crystal at high temperature. Using the Berry-phase method, we have also calculated the spontaneous polarization of temperature dependent cell structures, and find that our computational model provides a satisfactory description of the anomalous and so far unexplained rise in bulk electric polarization with temperature. Correlating the thermal motion induced lattice strain with temperature dependent spontaneous polarizations, we conclude that increasing thermal strain with temperatures combined with constrained thermal motion along the hydrogen bond motif are responsible of this increase in ferroelectricity at high temperature.

Reproducibility in density functional theory calculations of solids.

The widespread popularity of density functional theory has given rise to an extensive range of dedicated codes for predicting molecular and crystalline properties. However, each code implements the formalism in a different way, raising questions about the reproducibility of such predictions. We report the results of a community-wide effort that compared 15 solid-state codes, using 40 different potentials or basis set types, to assess the quality of the Perdew-Burke-Ernzerhof equations of state for 71 elemental crystals. We conclude that predictions from recent codes and pseudopotentials agree very well, with pairwise differences that are comparable to those between different high-precision experiments. Older methods, however, have less precise agreement. Our benchmark provides a framework for users and developers to document the precision of new applications and methodological improvements.