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Stacking mismatches in hexagonal boron nitride (h-BN) nanostructures affect their photonic, mechanical, and thermal properties. To access information about the stacked configuration of layered ensembles, highly sophisticated techniques like X-ray photoemission spectroscopy or electron microscopy are necessary. Here, instead, by taking advantage of the geometrical and chemical nature of h-BN, we show how simple structural models, based on shortened interplanar distances, can produce effective charge densities. Accounting these in the non-analytical part of the lattice dynamical description makes it possible to access information about the composition of differently stacked variants in experimental samples characterized by infrared spectroscopy. The results are obtained by density functional theory and confirmed by various functionals and pseudopotential approximations. Even though the method is shown using h-BN, the conclusions are more general and show how effective dielectric models can be considered as valuable theoretical pathways for the vibrational structure of any layered material.

Poly(3,4-ethylenedioxythiophene) (PEDOT) semiconductor plays a relevant role in the development of organic thermoelectric (TE) devices for low-power generation. While dopant counterions are usually needed to provide electrical conductivity, their overall effects on the thermoelectric response of the systems are unknown and uncontrolled. Here, we present a first principles study of the electronic and thermal transport of PEDOT crystalline assemblies, specifically analysing the role played by tosylate dopants on the thermoelectric figure of merit of the doped system. Our results demonstrate that, beside the desired charging effect, the presence of dopants impacts the bulk configuration by inflating the packing structure and worsening the intrinsic transport properties of the PEDOT host. This provides a rationale for the necessity of controlling the optimal amount and the structural incorporation of dopant in order to maximize the thermoelectric response of organic materials.

A series of compounds, featuring an ethenylic bridge and quinoline and isoquinoline end capping units possessing systematically varied substitution patterns, were prepared as molecular materials for electrochromic applications. The different structures were optimized in order to maximize the electrochromic contrast in the visible region, mostly by achieving a completely UV-absorbing oxidized state. Density functional theory (DFT) calculations are exploited in order to rationalize the correlation between the molecular structure, the functional groups' electronic properties, and the electrochemical behavior. It is shown that the molecular planarity (i.e. ring/ring π conjugation) plays a major role in defining the mechanism of the electrochemical charge transfer reaction, while the substituent's nature has an influence on the LUMO energy. Among the compounds here studied, the (E)-10-methyl-9-(2-(2-methylisoquinolinium-1-yl)-vinyl)-1,2,3,4-tetrahydroacri-dinium trifluoromethanesulfonate derivative shows the most interesting properties as an electrochromophore., Competing Interests: The authors declare no conflict of interest.

In this work, a series of eight thiophene-based polymers (exploited as "donors" in bulk heterojunction photovoltaics cells), whose structures were designed to be suitably tuned with the electronic characteristics of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), is considered,. The electronic properties of the mono-, di-, trimeric oligomers are reckoned (at the Hartree-Fock and DFT level of the theory) and compared to experimental spectroscopic and electrochemical results. Indeed, electrochemical and spectroscopic results show a systematic difference whose physical nature is assessed and related to the exciton (electron-hole) binding energy ( J e , h ). The critical comparison of the experimental and theoretical band gaps, i.e., the HOMO-LUMO energy difference, suggests that electrochemical and DFT values are the most suited to being used in the design of a polythiophene-based p-n junction for photovoltaics.

The dynamics of the early stage reaction between benzyl alcohol and Fe(acetylacetonate)3 is studied by exploiting the Dynamic Reaction Coordinate (DRC) approach, at the PBE0/6-31G* level of theory. Analysis of the DRC trajectory provides a detailed molecular insight into the catalytic effect observed in the acidic reaction environment, compared to the neutral one. The presence of an additional proton in the reaction system, meant to simulate an acidic reaction environment, dramatically affects the reaction path: both by decreasing the activation energy of the complex dissociation and leading to the formation of acetone.