Search results for "Density Functional Theory"
showing 10 items of 981 documents
Atomic and electronic structure of both perfect and nanostructured Ni(111) surfaces: First-principles calculations
2011
article i nfo In this study, we perform first principles simulations on both atomically smooth and nanostructured Ni(111) slabs. The latter contains periodically distributed nickel nanoclusters atop a thin metal film gradually growing from adatoms and serving as a promising catalyst. Applying the generalized gradient approximation within the formalism of the density functional theory we compare the atomic and electronic structures of Ni bulk, as well as both perfect and nanostructured (111) surfaces obtained using two different ab initio approaches: (i) the linear combination of atomic orbitals and (ii) the projector augmented plane waves. The most essential inter-atomic forces between the …
Linear scaling exchange gradients for Hartree–Fock and hybrid density functional theory
2000
Abstract A new method is introduced which allows to form the exchange part of self-consistent field energy gradients in a way which scales linearly with molecular size for molecules with a non-vanishing HOMO–LUMO gap. This is not only important for Hartree–Fock but as well for the popular hybrid density functional theory methods. The method preserves the optimized integral-driven structure of conventional direct methods. Efficiency and scaling behavior of the new method are illustrated for DNA fragments.
Canted Antiferromagnetism on Rectangular Layers of Fe2+ in Polymorphic CaFeSeO
2017
From stoichiometric amounts of CaO, Fe, and Se, pure powders and single crystals of quaternary Ca[FeSe2/2O2/2]∞2 can be obtained by solid-state reaction and self-flux growth, respectively. The as-synthesized compound exhibits a polymorphic crystal structure, where the two modifications have different stacking sequences of [FeSe2/2O2/2]2−∞2 layers. The two polymorphs have similar unit cells but different crystal symmetries (Cmc21 and Pnma), of which the former is non-centrosymmetric. Fe is divalent (d6) and high-spin, as proven by X-ray spectroscopy, Mossbauer spectroscopy, and powder neutron diffraction data. The latter two, in combination with magnetic susceptibility and specific heat data…
Radical cations and dications of bis[1]benzothieno[1,4]thiazine isomers
2021
Bis[1]benzothieno[1,4]thiazines (BBTT) are particularly electron-rich S,N-heteropentacenes and their radical cations and dications can be relevant intermediates in charge transport materials. All three regioisomers of N-p-fluorophenyl-BBTT (syn–syn, syn–anti, and anti–anti) were studied. A reliable preparation of radical cations and dications using antimony pentachloride as an oxidant gives deeply colored salts. The electronic structure of the radical cations was assessed by EPR spectroscopy, whereas dicationic structures were characterized by NMR spectroscopy. In addition, a deeper insight into the electronic structure was experimentally and computationally obtained by UV/Vis spectroscopy …
Rhodanine-based dyes absorbing in the entire visible spectrum
2017
A series of new broad-absorbing dyes based on rhodanine derivatives conjugated with triarylamines using Q5 a fluorene backbone was synthesized. Spectroscopic and electrochemical characterizations, along with theoretical calculations at the B3LYP/cc-pVDZ level, revealed interesting properties of the dyes, which make the dyes efficiently absorb in the entire visible spectrum.
The prediction of the nuclear quadrupole splitting of 119Sn Mössbauer spectroscopy data by scalar relativistic DFT calculations.
2006
The electric field gradient components for the tin nucleus of 34 tin compounds of experimentally known structures and Sn-119 Mossbauer spectroscopy parameters were computed at the scalar relativistic density functional theory level of approximation. The theoretical values of the electric field gradient components were used to determine a quantity, V, which is proportional to the nuclear quadrupole splitting parameter (Delta E). In a subsequent linear regression analysis the effective nuclear quadrupole moment, Q, was evaluated. The value of (11.9 +/- 0.1) fm(2) is a significant improvement over the non-relativistic result of (15.2 +/- 4.4) fm(2) and is in agreement with the experimental val…
Raman and theoretical study of the solvent effects on the sizable intramolecular charge transfer in the push-pull 5-(dimethylamino)-5'-nitro-2,2'-bit…
2006
In this paper, we analyze the degree of intramolecular charge transfer in a push-pull π-conjugated system, 5-(dimethylamino)-5'-nitro-2,2'-bithiophene, from changes in frequencies and relative intensities of its strongestRaman scatterings in a bunch of solvents with different polarities. Density functional theory (DFT) was used as a support of the experimental study. Solvent effects on the molecular and electronic structures and on the vibrational properties were estimated by performing B3LYP/6-31G** calculations within the framework of the polarized continuum model (PCM) developed by Tomasi. Calculations reveal that the molecule is highly polarized in the ground state and behaves as a very…
Theoretical investigation of paramagnetic group 13 diazabutadiene radicals: insights into the prediction and interpretation of EPR spectroscopy param…
2006
The electronic structures and the spin density distributions of the group 13 1,4-diaza(1,3)butadiene (DAB) radicals [(R-DAB)2M]˙, [(R-DAB)MX2]˙ and {[(R-DAB)MX]2}˙˙ (M = Al, Ga, In; X = F, Cl, Br, I; R = H, Me, tBu, Ph) are studied using density functional theory at both non-relativistic and relativistic levels of theory. The calculations demonstrate that all systems share a qualitatively similar electronic structure and are primarily ligand centred π-radicals. The calculated metal, nitrogen and hydrogen hyperfine couplings are found to be independent of the identity of the R-group and the halogen atom. They are, however, dependent on the geometry and oxidation state of the metal centre. Bo…
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…