Band gap control via tuning of inversion degree in CdIn2S4 spinel

Based on theoretical arguments, we propose a possible route for controlling the band-gap in the promising photovoltaic material CdIn2S4. Our ab initio calculations show that the experimental degree of inversion in this spinel (fraction of tetrahedral sites occupied by In) corresponds approximately to the equilibrium value given by the minimum of the theoretical inversion free energy at a typical synthesis temperature. Modification of this temperature, or of the cooling rate after synthesis, is then expected to change the inversion degree, which in turn sensitively tunes the electronic band-gap of the solid, as shown here by screened hybrid functional calculations.

Self-consistent relativistic band structure of the CH3NH3PbI3 perovskite

The electronic structure and properties of the orthorhombic phase of the CH 3 NH 3 PbI 3 perovskite are computed with density functional theory. The structure, optimized using a van der Waals functional, reproduces closely the unit cell volume. The experimental band gap is reproduced accurately by combining spin-orbit effects and a hybrid functional in which the fraction of exact exchange is tuned self-consistently to the optical dielectric constant. Including spin-orbit coupling strongly reduces the anisotropy of the effective mass tensor, predicting a low electron effective mass in all crystal directions. The computed binding energy of the unrelaxed exciton agrees with experimental data, and the values found imply a fast exciton dissociation at ambient temperature. Also polaron masses for the separated carriers are estimated. The values of all these parameters agree with recent indications that fast dynamics and large carrier diffusion lengths are key in the high photovoltaic efficiencies shown by these materials.

A syntactic and functional correspondence between reduction semantics and reduction-free full normalisers

Olivier Danvy and others have shown the syntactic correspondence between reduction semantics (a small-step semantics) and abstract machines, as well as the functional correspondence between reduction-free normalisers (a big-step semantics) and abstract machines. The correspondences are established by program transformation (so-called interderivation) techniques. A reduction semantics and a reduction-free normaliser are interderivable when the abstract machine obtained from them is the same. However, the correspondences fail when the underlying reduction strategy is hybrid, i.e., relies on another sub-strategy. Hybridisation is an essential structural property of full-reducing and complete strategies. Hybridisation is unproblematic in the functional correspondence. But in the syntactic correspondence the refocusing and inlining-of-iterate-function steps become context sensitive, preventing the refunctionalisation of the abstract machine. We show how to solve the problem and showcase the interderivation of normalisers for normal order, the standard, full-reducing and complete strategy of the pure lambda calculus. Our solution makes it possible to interderive, rather than contrive, full-reducing abstract machines. As expected, the machine we obtain is a variant of Pierre Crégut s full Krivine machine KN.