6 research outputs found
Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields
We apply Density Functional Theory (DFT) and the DFT+U technique to study the
adsorption of transition metal porphine molecules on atomistically flat Au(111)
surfaces. DFT calculations using the Perdew-Burke-Ernzerhof (PBE) exchange
correlation functional correctly predict the palladium porphine (PdP) low-spin
ground state. PdP is found to adsorb preferentially on gold in a flat geometry,
not in an edgewise geometry, in qualitative agreement with experiments on
substituted porphyrins. It exhibits no covalent bonding to Au(111), and the
binding energy is a small fraction of an eV. The DFT+U technique, parameterized
to B3LYP predicted spin state ordering of the Mn d-electrons, is found to be
crucial for reproducing the correct magnetic moment and geometry of the
isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111)
substantially alters the Mn ion spin state. Its interaction with the gold
substrate is stronger and more site-specific than PdP. The binding can be
partially reversed by applying an electric potential, which leads to
significant changes in the electronic and magnetic properties of adsorbed MnP,
and ~ 0.1 Angstrom, changes in the Mn-nitrogen distances within the porphine
macrocycle. We conjecture that this DFT+U approach may be a useful general
method for modeling first row transition metal ion complexes in a
condensed-matter setting.Comment: 14 pages, 6 figure
Forces between functionalized silica nanoparticles in solution
To prevent the flocculation and phase separation of nanoparticles in
solution, nanoparticles are often functionalized with short chain surfactants.
Here we present fully-atomistic molecular dynamics simulations which
characterize how these functional coatings affect the interactions between
nanoparticles and with the surrounding solvent. For 5 nm diameter silica
nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we
determined the hydrodynamic drag on two approaching nanoparticles moving
through solvent and on a single nanoparticle as it approaches a planar surface.
In most circumstances, acroscale fluid theory accurately predicts the drag on
these nano-scale particles. Good agreement is seen with Brenner's analytical
solutions for wall separations larger than the soft nanoparticle radius. For
two approaching coated nanoparticles, the solvent-mediated
(velocity-independent) and lubrication (velocity-dependent) forces are purely
repulsive and do not exhibit force oscillations that are typical of uncoated
rigid spheres.Comment: 4 pages, 3 fig
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Dynamics of Exchange at Gas-Zeolite Interfaces 1: Pure Component n-Butane and Isobutane
The authors present the results of molecular dynamics simulations of n-butane and isobutane in silicalite. They begin with a comparison of the bulk adsorption and diffusion properties for two different parameterizations of the interaction potential between the hydrocarbon species, both of which have been shown to reproduce experimental gas-liquid coexistence curves. They examine diffusion as a function of the loading of the zeolite, as well as the temperature dependence of the diffusion constant at loading and for infinite dilution. They continue with simulations in which interfaces are formed between single component gases and the zeolite. After reaching equilibrium, they examine the dynamics of exchange between the bulk gas and the zeolite. Finally, they calculate the permeability of the zeolite for n-butane and isobutane as a function of pressure. Their simulations are performed for a number of different gas temperatures and pressures, covering a wide range of state points