σ-Hole intermolecular interactions between carbon oxides and dihalogens: Ab-initio investigations.

Recently, halogen bonding (XB) has received increased attention as a new type of non-covalent interaction widely present in nature. In this work, quantum chemical calculations at DFT level have been carried out to investigate halogen bonding interactions between COn (n = 1 or 2) and dihalogen molecules XY (X = F, Cl, Br, I and Y = Cl, Br, I). Highly accurate all-electron data, estimated by CCSD(T) calculations, were used to benchmark the different levels of computational methods with the objective of finding the best accuracy/computational cost. Molecular electrostatic potential, interaction energy values, charge transfer, UV spectra, and natural bond orbital (NBO) analysis were determined to better understand the nature of the XB interaction. Density of states (DOS) and projected DOS were also computed. Hence, according to these results, the magnitude of the halogen bonding is affected by the halogen polarizability and electronegativity, where for the more polarizable and less electronegative halogen atoms, the σ-hole is bigger. Furthermore, for the halogen-bonded complexes involving CO and XY, the OC∙∙∙XY interaction is stronger than the CO∙∙∙XY interaction. Thus, the results presented here can establish fundamental characteristics of halogen bonding in media, which would be very helpful for applying this noncovalent interaction for the sustainable capture of carbon oxides.

Metallo-dithiaporphyrin pigments for bulk-heterojunction solar cell applications: ab initio investigation of structural and optoelectronic properties.

Metallo-dithiaporphyrin small molecules have been designed by substituting Ru(ii) with various transition metals at the same oxidation state (M = Mn, Fe, Ni, Cu) as donor materials for Bulk Heterojunction Organic Solar Cells (BHJ-OSCs). Density functional theory (DFT) and time-dependent DFT (TD-DFT) have been used to study the optoelectronic properties of metallo-dithiaporphyrin at various functionals and basis sets. We discovered that the open-circuit voltage (VOC) value increases when Ru(ii) in Ru(S2TTP)Cl2 (S2TTP = tetra-p-tolyldithiaporphyrin) is substituted. In addition, the light harvesting efficiency (LHE) of nickel, manganese, and iron complexes was found to be similar to that of ruthenium, and the iron complex furthermore presented a comparable charge transfer in the excited state corresponding to the Q-band, compared to Ru(S2TTP)Cl2. Hence M(S2TTP)Cl2 (M = Mn, Fe, Ni) appear to be potential low cost candidate donor molecules within a bulk heterojunction solar cell. We further propose suitable engineered acceptor pigments, fitted to provide a good overall solar cell efficiency.