Search results for "Functional theory"
showing 10 items of 1012 documents
Ultrafast Twisting of the Indoline Donor Unit Utilized in Solar Cell Dyes: Experimental and Theoretical Studies
2015
Previous time-resolved measurements on D149, the most-studied dye of the indoline family, had shown a fast time-component of 20–40 ps that had tentatively been attributed to structural relaxation. Using femtosecond transient absorption, we have investigated the isolated indoline donor unit (i.e., without acceptor group) and found an ultrafast decay characterized by two lifetimes of 3.5 and 23 ps. Density functional theory calculations show π-bonding and π*-antibonding character of the central ethylene group for the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The LUMO is localized on the flexible vinyl-diphenyl region of the donor unit and a twist…
Solvatochromy and symmetry breaking in two quadrupolar oligophenylenevinylenes
2020
Electrooptical absorption measurements (EOAM), solvatochromic dependences and quantum chemical simulations testify to large dipole moments change of two quadrupolar oligophenylenevinylenes upon transition to Franck-Condon excited state μeFC. The values of the dipole moments μg and μeFC are in the range [(4.2 - 4.9)1030] C m and (30.8 - 47.0)1030C m, respectively. The relations of dipole moments in the ground and excited states determined by EOAM correlate well with results obtained via the solvatochromic method. Calculations carried out by density functional theory (DFT) show that optimized configuration of the ground state of these molecules is not planar. The results from all methods appl…
Adsorption and activation of O2 at Au chains on MgO/Mo thin films
2010
We have investigated the adsorption of O(2) on Au(n) clusters (n = 1-6) supported by an ultra thin (3ML)MgO(001) film on Mo metal via density functional theory calculations. On thin films, these small clusters have chain like structures and their electronic states resemble 1D quantum well states. The Au(1-3) are charged by one electron whereas the larger Au(4-6) get two electrons from the substrate. This is confirmed both by the symmetries of the HOMO and LUMO states of the clusters and the Bader charge analysis. In contrast to the O(2) adsorption on gas-phase clusters, the adsorption energy of O(2) molecule does not show pronounced oscillations as a function of cluster size. The O(2) is ac…
Towards multifunctional magnetic systems through molecular-programmed self assembly of Re(IV) metalloligands
2015
Abstract The molecular-programmed approach based on the use as ligands of tailor-made metalloligands containing stable six-coordinate rhenium(IV) as paramagnetic centres is presented in this review article. A relatively large amount of spin density is covalent-delocalized away from the rhenium to the peripheral atoms of the ligands in the case of the Re(IV) metalloligands, as shown by polarized neutron diffraction experiments and density functional theory calculations. This feature accounts for the significant through space-magnetic interactions that occur in most of its mononuclear species and more interestingly it also explains the strengthening of the magnetic interactions in the heterom…
A 58-electron superatom-complex model for the magic phosphine-protected gold clusters (Schmid-gold, Nanogold®) of 1.4-nm dimension
2011
We have re-investigated the structural identity of the famous gold-phosphine-halide Au:PR3:X compound having 55–69 gold atoms and core size of 1.4 nm (similar to “Schmid gold” or Nanogold®) from the viewpoint of the Superatom-Complex (SAC) model for ligand protected metal clusters, and in consideration of the ligand-adatom groups observed previously for the structurally known 39-atom cluster [Au39(PR3)14Cl6]−1. Density functional theory is used to define the formation energy of various compositions and structures, enabling a comparison of the stability of different cluster-sizes. In agreement with the SAC model, we find a strong correlation between optimal energy and delocalized electron sh…
Cluster-model density functional study of a W–Cu(100) STM junction
1999
Abstract In this article, we investigate the electronic properties of different clusters modelling a tungsten tip, the Cu(1 0 0) surface and interacting W–Cu(1 0 0) systems in STM configuration. Electronic structure calculations are carried out within the LDA approximation of the Density Functional Theory (DFT). Both integrated (densities of states) and local properties (electronic density and electrostatic potential) are considered. The study is performed for top and hollow surface sites and two different tip–sample separations.
Thiolate Adsorption on Au(hkl) and Equilibrium Shape of Large Thiolate-covered Gold Nanoparticles
2013
The adsorption of thiolates on Au surfaces employing density-functional-theory calculations has been studied. The dissociative chemisorption of dimethyl disulfide (CH3S−SCH3) on 14 different Au(hkl) is used as a model system. We discuss trends on adsorption energies, bond lengths, and bond angles as the surface structure changes, considering every possible Au(hkl) with h, k, l ≤ 3 plus the kinked Au(421). Methanethiolate (CH3S-) prefers adsorption on bridge sites on all surfaces considered; hollow and on top sites are highly unfavourable. The interface tensions for Au(hkl)-thiolate interfaces is determined at low coverage. Using the interface tensions in a Wulff construction method, we cons…
Dyes That Bear Thiazolylazo Groups as Chromogenic Chemosensors for Metal Cations
2011
A family of dyes (L 1-L 6) that contain a thiazolylazo group as signalling subunit and several macrocyclic cavities with different ring sizes and type and number of heteroatoms as binding sites has been synthesized and characterized. Solutions of L 1-L 6 in acetonitrile show broad and structureless absorption bands in the 554-577 nm range with typicalmolar absorption coefficients that range from 20000 to 32000 M -1 cm -1. A detailed protonation study was carried out with solutions of L 1, L 2 and L 5 in acetonitrile. Addition of one equivalent of protons to L 1 and L 2 resulted in the development of a new band at 425 and 370 nm, respectively, which was ascribed to protonation in the aniline…
Similarity and Specificity of Chlorophyll b Triplet State in Comparison to Chlorophyll a as Revealed by EPR/ENDOR and DFT Calculations
2019
An investigation of the photoexcited triplet state of chlorophyll (Chl) b has been carried out by means of electron nuclear double resonance, both in a frozen organic solvent and in a protein environment provided by the water-soluble chlorophyll protein of Lepidium virginicum. Density functional theory calculations have allowed the complete assignment of the observed hyperfine couplings corresponding to the methine protons and the methyl groups, leading to a complete picture of the spin density distribution of the triplet state in the tetrapyrrole macrocycle. The triplet-state properties of Chl b are found to be similar, in many respects, to those previously reported for Chl a, although som…
Strong circularly polarized luminescence of an octahedral chromium(iii) complex
2019
The chiral spin-flip luminophore [Cr(ddpd)2]3+ can be resolved into enantiopure material by chiral HPLC. The corresponding enantiomers show very high luminescence dissymmetry factors of up to ∣glum ∣≈ 0.093 in circularly polarized luminescence (CPL) measurements for the "ruby-like" phosphorescence transition 2E/2T1 → 4A2 in the near-IR region around λ ≈ 775 nm.