Search results for "Density Functional Theory"
showing 10 items of 981 documents
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…
Unveiling the Different Reactivity of Bent and Linear Three-Atom-Components Participating in [3 + 2] Cycloaddition Reactions
2021
The reactivity of a series of pairs of bent and linear three-atom-component (B-TACs and L-TACs) participating in [3 + 2] cycloaddition (32CA) reactions towards ethylene and electrophilic dicyanoethylene (DCE) have been studied within the Molecular Electron Density Theory. While the pseudodiradical structure of B-TACs changes to that of pseudoradical or carbenoid L-TACs upon dehydrogenation, zwitterionic B-TACs remain unchanged. Conceptual Density Functional Theory (CDFT) indices characterize five of the nine TACs as strong nucleophiles participating in polar reactions towards electrophilic ethylenes. The activation energies of the 32CA reactions with electrophilic DCE range from 0.5 to 22.0…
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…
Selective Acrolein Hydrogenation over Ligand-Protected Gold Clusters : A Venus Flytrap Mechanism
2022
The catalytic partial hydrogenation of α,β-unsaturated aldehydes is an ideal reaction to understand the selectivity between two different functional groups Here the two functional groups are C═C and C═O, and the hydrogenation of C═O is preferentially desired due to the importance of the issuing products, unsaturated alcohols, in fine-chemical industries. Using density functional theory calculations, we investigate the catalytic competency toward this reaction of a Au nanocluster in the presence of protecting ligands that offer higher stability and the possibility for the uniform distribution of size-selected clusters in the catalytic system. meta-Mercaptobenzoic-acid-protected-protected Au …
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 …
Theoretical Studies of the Reactivity of Cyclopentadienyl Nitrosyl Alkyl Species of Molybdenum and Tungsten
2000
International audience; The reactivity differences observed experimentally for Cp*W(NO)(CH2CMe3)2 and CpMo(NO)(CH2CMe3)2 have been investigated using density functional theory (DFT) techniques. The reactions of the CpW(NO)(CH2) model complex with NH3 and CH4 are more exothermic and have lower activation barriers than the corresponding processes for CpMo(NO)(CH2). The η2(C,H) methane complex CpM(NO)(CH2)(CH4) (M = Mo, W) can undergo two competitive processes: C−H activation to afford CpM(NO)(CH3)2 or loss of methane. The relative barrier heights are almost identical for M = W, whereas the formation of CpM(NO)(CH3)2 is significantly disfavored for M = Mo. The activation of C−H and N−H bonds …
Tri- and tetranuclear heteropivalate complexes with core {Fe2Ni O} (x = 1, 2): Synthesis, structure, magnetic and thermal properties
2019
Abstract The reactions of complex [Fe2Ni(O)(Piv)6(Et2O)(H2O)2] (1) with 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy) gave the following new coordination compounds: the trinuclear complex [Fe2Ni(O)(Piv)6(phen)H2O]·(C2H5)2O (2), the tetranuclear ones [Fe2Ni2(OH)2(Piv)8(phen)2] (3) and [Fe2Ni2(OH)2(Piv)8(bpy)2] (4), depending on the crystallization conditions. According to single crystal X-ray diffraction data, all the compounds have molecular structures. The Mossbauer spectra of 1–3 correspond to high-spin Fe3+ ions in an octahedral environment consisting of oxygen atoms. The DC magnetic susceptibility studies and quantum-chemical analysis of intra- and intermolecular J pathways using…
2,4,5-Trimethylimidazolium Scaffold for Anion Recognition Receptors Acting Through Charge-Assisted Aliphatic and Aromatic C–H Interactions
2016
A series of two-armed 2,4,5-trimethylimidazolium-based oxoanion receptors, which incorporate two end-capped photoactive anthracene rings, being the central core an aromatic or heteroaromatic ring, has been designed. In the presence of HP2O7(3-), H2PO4(-), and SO4(2-) anions, (1)H- and (31)P NMR spectroscopical data clearly indicate the simultaneous occurrence of several charge-assisted aliphatic and aromatic C-H noncovalent interactions, i.e., significant downfield shifts were observed for the imidazolium C(2)-CH3 protons, the methylene N-CH2 protons, and the inner aromatic proton or the outer heteroaromatic protons. Density functional theory calculations confirm the occurrence of these non…