Search results for "Density Functional Theory"

Experimental and theoretical study of stereoelectronic and H-bond control of reactivity in α- and β-methyl d-glucopyranoside ozonolysis

1998

Abstract The topography of the molecular electrostatic potential (MEP) of α and β anomers of methyl d -glucopyranosides has been used to analyze the reactivity of these species towards electrophilic attack and to complete the results we obtained during the ozonation reaction. Molecular mechanics (MM) and molecular dynamics (MD) simulations have been performed to screen the conformational space of α- and β-methyl d -glucopyranosides in order to determine the chair conformations which correspond to a global minimum energy conformation. Density Functional Theory (DFT) (Faststructure) and PM3 (semiempirical) calculations have been carried out to refine the geometries of the 4 C 1 and 1 C 4 chai…

ChemInform Abstract: Electrochemical Synthesis of 2-Arylimino-4,5-di(2-furyl)-1,3-dioxoles and (E)-1,2-Di(2-furyl)vinylene Bis(N-arylchloroformimidat…

2009

Abstract Cathodic reductions of 2,2′-furils in the presence of N-arylcarbonimidoyl dichlorides lead to 2-arylimino-4,5-di(2-furyl)-1,3-dioxoles in high yields, along with minor amounts of (E)-1,2-di(2-furyl)vinylene bis(N-arylchloroformimidates). HF and B3LYP density functional theory methods have been applied to the determination of molecular geometries and to study the topomerization mechanism of aryliminodioxoles. The molecular structure of (E)-1,2-di(2-furyl)vinylene bis[N-(2-chloro-4-methylphenyl)chloroformimidate] has been determined by X-ray crystallography and compared with the calculated structure.

Diene-Containing Half-Sandwich MoIII Complexes as Ethylene Polymerization Catalysts: Experimental and Theoretical Studies

2001

International audience; Seventeen-electron compounds of Mo III having the general formula [(h 5-C 5 R 5)Mo(h 4-diene)X 2 ] (R H, Me; diene butadiene, iso-prene, or 2,3-dimethylbutadiene; X Cl, CH 3) are a new class of ethylene polymerization catalysts. The polyethy-lene obtained shows a bimodal distribution , the major weight fraction being characterized by very long (M around 10 6) and highly linear polymer chains. The newly prepared pentamethylcyclo-pentadienyl (Cp*) derivatives are more active than the cyclopentadienyl (Cp) derivatives, but much less active than previously investigated niobium III compounds having the same stoichiometry. On the other hand, the turnover frequency of the a…

2015

AbstractWhile understanding the properties of materials under stress is fundamentally important, designing experiments to probe the effects of large tensile stress is difficult. Here tensile stress is created in thin films of potassium (up to 4 atomic layers) by epitaxial growth on a rigid support, graphite. We find that this “simple” metal shows a long-range, periodic “herringbone” reconstruction, observed in 2- and 3- (but not 1- and 4-) layer films by low-temperature scanning tunneling microscopy (STM). Such a pattern has never been observed in a simple metal. Density functional theory (DFT)simulations indicate that the reconstruction consists of self-aligned stripes of enhanced atom den…

Electron microscopy of gold nanoparticles at atomic resolution

2014

Detailed structure of a gold nanoparticle Adding only a few atoms or changing the capping ligand can dramatically change the structure of individual metal nanoparticles. Azubel et al. used aberration-corrected transmission electron microscopy to derive a three-dimensional reconstruction of water-soluble gold nanoparticles. Small-angle x-ray scattering and other techniques have also corroborated this model. They used this to determine the atomic structure, which compared favorably with density functional theory calculations, without assuming any a priori structural knowledge or the use of model fitting. Science , this issue p. 909

On deterministic solutions for multi-marginal optimal transport with Coulomb cost

2022

In this paper we study the three-marginal optimal mass transportation problem for the Coulomb cost on the plane $\R^2$. The key question is the optimality of the so-called Seidl map, first disproved by Colombo and Stra. We generalize the partial positive result obtained by Colombo and Stra and give a necessary and sufficient condition for the radial Coulomb cost to coincide with a much simpler cost that corresponds to the situation where all three particles are aligned. Moreover, we produce an infinite class of regular counterexamples to the optimality of this family of maps.

Probing Surface Quantum Flows in Deformed Pygmy Dipole Modes

2017

In order to explore the nature of collective modes in weakly bound nuclei, we have investigated deformation effects and surface flow patterns of isovector dipole modes in a shape-coexisting nucleus $^{40}$Mg. The calculations were done in a fully self-consistent continuum finite-amplitude Quasiparticle Random Phase Approximation (QRPA) in a large deformed spatial mesh. An unexpected result of pygmy and giant dipole modes having disproportionate deformation splittings in strength functions was obtained. Furthermore, the transition current densities demonstrate that the long-sought core-halo oscillation in pygmy resonances is collective and compressional, corresponding to the lowest excitatio…

Ag44(SeR)30: A Hollow Cage Silver Cluster with Selenolate Protection.

2015

Selenolate protected, stable and atomically precise, hollow silver cluster was synthesized using solid state as well as solution state routes. The optical absorption spectrum shows multiple and sharp features similar to the thiolated Ag44 cluster, Ag44(SR)30 whose experimental structure was reported recently. High-resolution electrospray ionization mass spectrometry (HRESI MS) shows well-defined molecular ion features with two, three, and four ions with isotopic resolution, due to Ag44(SePh) 30. Additional characterization with diverse tools confirmed the composition. The closed-shell 18 electron superatom electronic structure, analogous to Ag44(SR)30 stabilizes the dodecahedral cage with a…

Ligand-Protected Gold Nanoclusters as Superatoms—Insights from Theory and Computations

2012

Abstract Gold clusters and nanoparticles, stabilized by various ligands, exhibit a rich array of interesting and important electronic, optical, chemical and catalytic properties. Many particles can now be synthesized by wet chemistry, and they can be handled as normal chemicals: stored, modified and functionalized for applications in medical therapy, biolabelling, sensing, nanoelectronics and catalysis. In recent years, understanding of the stability, surface chemistry and functionalization of these interesting building blocks of nano-matter has taken a quantum leap. This is facilitated by simultaneous breakthroughs in experimental and theoretical fronts concerning accurate structural deter…

Formation of linear Ni nanochains inside carbon nanotubes: Prediction from density functional theory

2013

Abstract First principles calculations have been performed to investigate the ground state properties of monoperiodic single-walled carbon nanotubes (CNTs) containing nanochain of aligned Ni atoms inside. Using the PBE exchange-correlation functional ( E xc ) within the framework of density functional theory (DFT) we predict the clusterization of Ni filaments in ( n ,0) CNTs for n ⩾  9 and for ( n , n ) CNTs for n ⩾  6. The variations in formation energies obtained for equilibrium defective nanostructures allow us to predict the most stable Ni@CNT compositions. Finally, the electronic charge redistribution has been calculated in order to explore intermolecular properties leading to stronger…