Search results for "Density Functional Theory."
showing 10 items of 935 documents
Towards Iron(II) Complexes with Octahedral Geometry: Synthesis, Structure and Photophysical Properties
2020
The control of ligand-field splitting in iron (II) complexes is critical to slow down the metal-to-ligand charge transfer (MLCT)-excited states deactivation pathways. The gap between the metal-centered states is maximal when the coordination sphere of the complex approaches an ideal octahedral geometry. Two new iron(II) complexes (C1 and C2), prepared from pyridylNHC and pyridylquinoline type ligands, respectively, have a near-perfect octahedral coordination of the metal. The photophysics of the complexes have been further investigated by means of ultrafast spectroscopy and TD-DFT modeling. For C1, it is shown that&mdash
A Hirshfeld partitioning of polarizabilities of water clusters
2006
International audience; A new Hirshfeld partitioning of cluster polarizability into intrinsic polarizabilities and charge delocalization contributions is presented. For water clusters, density-functional theory calculations demonstrate that the total polarizability of a water molecule in a cluster depends upon the number and type of hydrogen bonds the molecule makes with its neighbors. The intrinsic contribution to the molecular polarizability is transferable between water molecules displaying the same H-bond scheme in clusters of different sizes, and geometries, while the charge delocalization contribution also depends on the cluster size. These results could be used to improve the existin…
Symmetry breakings in a metal organic framework with a confined guest
2020
The MOF $[{\text{Fe(tvp)}}_{2}{(\text{NCS})}_{2}]\ifmmode\cdot\else\textperiodcentered\fi{}2\text{BzCHO}$ is demonstrated to undergo a complex sequence of phase transitions and spin-crossover behavior of its constitutive ${\text{Fe}}^{\text{II}}$ ions upon adsorption of benzaldehyde guest molecules. Our study, combining Raman and synchrotron x-ray diffraction measurements on a single crystal, reveals that the conversion from the pure high-spin to the pure low-spin phases implies a rich sequence of intermediate phases, with symmetry breaking forming at least three different space groups. These different symmetries involve spin-state ordering, ligand ordering, and guest ordering, interpreted …
Theoretical use of boron nitride nanotubes as a perfect container for anticancer molecules
2016
International audience; In recent years great interest has emerged in the development of nanocarriers for drug transport. One of themajor challenges is to obtain a drug delivery system able to control the drug release profile, transportabsorption and distribution, in the view of improving efficacy and safety. Herein, we present theoreticalresults based on density functional theory (DFT) to determine the best adsorption site for the anticancerifosfamide molecule in boron nitride nanotubes. For this functionalized system we determine thedependence of the adsorption energy on the displacement of molecules in the outer and inner boronnitride surfaces, together with their local morphological and…
Switch in Relative Stability between cis and trans 2-Butene on Pt(111) as a Function of Experimental Conditions: A Density Functional Theory Study
2018
International audience; The adsorption of cis and trans 2-butenes on Pt(111) has been studied as a function of hydrogen coverage OH by means of calculations based on density functional theory (DFT) with the inclusion of dispersion forces. All hydrogen coverages have been considered, from 0 to 1.00 monolayer (ML). For each case, the di-sigma and pi adsorption geometries of the olefins have been compared at a surface coverage of theta(C4H8) = 0.11 ML. Calculations of the Gibbs free energies of these systems have identified the most stable 2-butene isomer (cis or trans) as a function of coverage, temperature, and pressure. In particular, focus was placed on two sets of conditions, namely, one …
A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters.
2014
We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like elec…
Modelling the effect of nuclear motion on the attosecond time-resolved photoelectron spectra of ethylene
2014
arXiv:1403.5408
Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid
2017
Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1–3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68–144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic reson…
Density Functional Theory Investigation on the Nucleation and Growth of Small Palladium Clusters on a Hyper-Cross-Linked Polystyrene Matrix
2014
Density functional theory calculations were employed to investigate the nucleation and growth of small palladium clusters, up to Pd9, into a microcavity of the porous hyper-cross-linked polystyrene (HPS). The geometries and the electronic structures of the palladium clusters inside the HPS cavity, following the one-by-one atom addition, are affected by a counterbalance between the Pd–phenyl (Pd−Φ) and Pd–Pd interactions. The analysis performed on energetics, cavity distortions, and cluster geometries indeed suggest that the cluster growth is dominated by the Pd−Φ interactions up to the formation of Pd4 aggregates, whereas the metal–metal interactions actually rule the growth of the larger c…
Lithium Cation-Catalyzed Benzene Diels-Alder Reaction: Insights on the Molecular Mechanism Within the Molecular Electron Density Theory.
2020
The lithium cation Li+-catalyzed Diels-Alder (DA) reactions of benzene toward a series of acetylenes of improved nucleophilicity can be described within the context of the molecular electron density theory (MEDT) at the ωB97XD/6-311G(d,p) level. Conceptual density functional theory indices characterize the crown ether solvated complex benzene-lithium Bz-Li-Cro as a superelectrophile. Coordination of a lithium cation to benzene does not change substantially the electron localization function electronic structure of benzene. The DA reaction of Bz-Li-Cro with acetylene shows a reduction of the energy of activation of 6.9 kcal·mol-1, which is not sufficient for the reaction to take place, thus …