Accurate predictions of the electronic excited states of BODIPY based dye sensitizers using spin-component-scaled double-hybrid functionals: a TD-DFT benchmark study.

The vertical excitation energies of 13 BODIPY based dye sensitizers are benchmarked by means of TD-DFT, using 36 functionals from different DFT rungs. Most TD-DFT results were found to overestimate the excitation energies, and show mean absolute error (MAE) values in the range 0.2-0.5 eV. The dispersion-corrected, spin-component-scaled, double-hybrid (DSD) functionals DSD-BLYP and DSD-PBEP86 were found to have the smallest MAE values of 0.083 eV and 0.106 eV, respectively, which is close to the range of average errors found in the more expensive coupled-cluster methods. Moreover, DSD-BLYP and DSD-PBEP86 functionals show excellent consistency and quality of results (standard deviation = 0.048 eV and 0.069 eV respectively). However, the range separated hybrid (RSH) and the range separated double hybrid (RSDH) functionals were found to provide the best predictability (linear determination coefficient R 2 > 0.97 eV).

Thiacrown Ethers Engaged C60 through Charge Transfer: Experimental and Theoretical Study.

UV-Vis spectroscopy is used to study the charge transfer complexes of thiacrown ethers 1-6 with fullerene. The size of TCE1-6 and the nature of the heteroatoms (N, O and S) have been systematically changed to examine the effect of these factors on the HOMO/LUMO energy levels, the optical energy gap and the interactions between TCE's and C60. The negative and positive values of ΔS designate the structural forming method and the randomness of the free solvent molecules, respectively. Thermodynamics and stability data show that the complexes have a 1:1 ratio that has been emphasized by density functional theory calculations. Additionally, they show a synergetic interplay of donor-acceptor, π-π, and n-π interactions, which are the basis for the affinity of our novel receptors toward C60. The proposed system of enzyme model suggests a development concept in the future design of enzyme model organic photovoltaic systems.

Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine.

A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Different mechanistic pathways were studied for the reaction of n-propylamine. Both thermodynamic functions and activation parameters were calculated for all investigated pathways. Most of the dehydrogenation reaction mechanisms occur in a concerted step transition state as an exothermic process. The mechanisms for pathways A and B comprise two key-steps: H2 eliminated from PA leading to the formation of allylamine that undergoes an unimolecular dissociation in the second step of the mechanism. Among these pathways, the formation of ethyl cyanide and H2 is the most significant one (pathway B), both kinetically and thermodynamically, with an energy barrier of 416 kJ mol-1. The individual mechanisms for the pathways from C to N involve the dehydrogenation reaction of PA via hydrogen ion, ammonia ion and methyl cation. The formation of α-propylamine cation and NH3 (pathway E) is the most favorable reaction with an activation barrier of 1 kJ mol-1. This pathway has the lowest activation energy calculated of all proposed pathways.

The rational design of a Au(I) precursor for focused electron beam induced deposition.

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au-Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe3, they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe3 and MeAuPMe3 shows that Au-Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au-Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au.

Structures, electronic properties and stability phase diagrams for copper(I/II) bromide surfaces.

This study presents a comprehensive periodic slab DFT investigation into structures, electronic properties and thermodynamic stability of all plausible terminations of CuBr and CuBr2 surfaces. We first estimate lattice constants, formation and cohesive energies for the two bulk copper bromides before proceeding to analyse geometrical and electronic features of CuBr and CuBr2 configurations. Surface geometries exhibit, to a large extent, corresponding bulk structures. Nevertheless, certain CuBr2 surfaces experience a downward displacement of the topmost Cu-containing layers. We plot total and projected density of states for bulk and surface geometries of these two copper bromides and calculate their associated Bader's electronic charges. Electronic structure analysis for the bulk and surfaces of these two copper bromides show that CuBr bulk and its most stable surface (CuBr(001)_Br) do not exhibit any metallic character, whereas CuBr2 bulk and its most stable surface (CuBr2(001)_Br) both exhibit metallic characters. The formalism of the ab initio atomistic thermodynamics affords the construction of energy phase diagrams. We predict that the CuBr(001) surface, truncated with Br atoms, is the most stable structure among the considered CuBr slabs at all physically meaningful ranges of the chemical potential of bromine. This surface resembles a c(2 × 2)-bromine sheet that was characterised experimentally from initial interaction of Br2 with a Cu(100) surface. We find that surfaces terminated with the electronegative bromine atoms, if accompanied by significant relaxation, tend to be more stable. Calculated surface energies predict the shapes of CuBr and CuBr2 nanoparticles as the chemical potential of bromine changes.

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra.

The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.