M.M. Assem

Theoretical characterisation of highly efficient dye-sensitised solar cells

Molecular electronic structure calculations, employing density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methodologies, have been carried out to improve the performance of the synthesised dye YD2-o-C8 which is characterised by 11.9%–12.7% efficiencies. We aimed to narrow the band gap of YD2-o-C8 to extend the light-harvesting region to near-infrared (NIR). This was done by incorporating Cd instead of Zn onto the porphyrin ring and elongating the length of π-conjugation by adding ethynylene link and anthracene unit, so that the performances of the suggested cells could be expected to exceed the 11.9%–12.7% efficiencies with TiO2, ZnO2, and WO3 oxide electrodes. The effects of modifying the central metal and elongating the length of π-conjugation on cell performance are confirmed in terms of frontier molecular orbital (FMO) energy gaps, density of states (DOS), molecular electrostatic potentials (MEPs), non-linear optical (NLO) properties, ultraviolet–visible (UV–vis) electronic absorption, and 1H nuclear magnetic resonance chemical shifts. Increasing the length of π-conjugation of the D–π–A dyes leads to increasing the DOS near Fermi levels, more active NLO performance, strong response to the external electric field, delocalisation of the negative charges near the anchoring groups, deep electron injection, suppressing macrocycle aggregation, active dye regeneration, and inhibited dye recombination. The calculated band gap/eV of the present DMP-Zn is correlated with the experimental (E1/2(oxidation)–E1/2(reduction)/V) potentials of the identical YD2-o-C8. A co-sensitiser is suggested for NIR sensitisation (550–950 nm) to increase the power-to-conversion efficiency beyond 14%.

Magnetic and binding properties of Co-doped single-walled carbon nanotubes: a first principles study

An attempt has been made to analyze the magnetic-spin quenching property of Co, as a representative of transition metals, in Co-doped single-walled carbon nanotubes (SWCNTs) as well as the binding property of CO with the side walls of the Co-doped SWCNTs by means of hybrid density functional theory (DFT) calculations. Four different types of SWCNTs are considered: semi-conducting (5,0) zigzag, metallic (5,2) and semi conducting (5,3) chirals, and metallic (5,5) armchair. The results show that while the spin states of Co in the whole of the present Co-doped SWCNTs were preserved, the combined effects of adsorbate (CO) and substrate (Co-doped SWCNT) were strong enough to favor the low-spin states, and to quench the spins in the Co-doped SWCNTs (5,0) and (5,2). The doped Co atom converts the endothermic reactions of CO molecules on the outer surfaces of the pure SWCNTs into exothermic reactions. The nature of charge transfer between the d-orbitals of Co, and the π* orbital of the nearby C of CO is clarified. Natural bond orbital (NBO) analysis reveals that the electronic configuration of the doped Co metal represents a qualitative change with respect to that of the free-metal. The binding of CO precursor is mostly dominated by the metal E(i)Co..CO pairwise additive contributions, and the role of the SWCNTs is not restricted to supporting the metal. The spin quenched SWCNTs are characterized in terms of isodensity contours of frontier orbitals. Molecular electrostatic potentials (MEPs) indicate that SWCNTs can act as effective gas sensors for nucleophiles. The results show that Co-doped SWCNTs can be useful in spintronics applications and sensor technology.

Spin transition energies of Cr in complexes and CO binding with Cr deposited on S2− and Se2− anion impurities of MgO (001) surface density functional theory calculations

An attempt has been made to analyze the spin transition energies of Cr, a representative example of transition metals, in a variety of complexes formed at regular (001) surfaces of MgO, as well as the adsorption of CO by means of hybrid density functional theory calculations and embedded cluster models. Clusters of moderate sizes are embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces. While the spin states of Cr are reduced and preserved in all complexes, be they defect-free or-defect containing, the combined effects of the adsorbate and the substrate in the defect-free OC.Cr.Mg9O13O2− complex were strong enough to favor the low-spin state and to quench the spin. The deposited Cr atoms enhance the adsorption of CO. The significant weakening of bond strength between OC and Cr in complexes supports the concept of bond order conservation. The natural bond orbital (NBO) analysis reveals that the electronic structure of the adsorbed metal represents a qualitative change with respect to that of the free metal. The effects of spin contamination on the geometry, Mulliken charges and adsorption energy are examined. The binding of CO precursor is dominated by the E (i)Cr.CO pairwise additive components, and the role of the support was not restricted to supporting the metal. Relations are established between the process of spin transition and the energy gaps between frontier orbitals. The results show that the spin state of adsorbed metal atoms on oxide supports and the role of precursor molecules in the properties of spin transition energies of Cr in complexes need to be explicitly taken into account.