A combinatorial approach to the electron correlation problem

Starting from a path-integral formulation of quantum statistical mechanics expressed in a space of Slater determinants, we develop a method for the Monte Carlo evaluation of the energy of a correlated electronic system. The path-integral expression for the partition function is written as a contracted sum over graphs. A graph is a set of distinct connected determinants on which paths can be represented. The weight of a graph is given by the sum over exponentially large numbers of paths which visit the vertices of the graph. We show that these weights are analytically computable using combinatorial techniques, and they turn out to be sufficiently well behaved to allow stable Monte Carlo simulations in which graphs are stochastically sampled according to a Metropolis algorithm. In the present formulation, graphs of up to four vertices have been included. In a Hartree-Fock basis, this allows for paths which include up to sixfold excitations relative to the Hartree-Fock determinant. As an illustration, we have studied the dissociation curve of the N(2) molecule in a VDZ basis, which allows comparison with full configuration-interaction calculations.     

Controlling organic reactions on silicon surfaces with a scanning tunneling microscope: theoretical and experimental studies of resonance-mediated desorption

The dynamics of tip-induced, resonance-mediated bond-breaking in complex organic adsorbates is studied theoretically and experimentally. Desorption of benzene from a Si(100) surface is found to be efficient and sensitive to voltage, the measured yield rising from below 10(-10) to ca. 10(-6) per electron within a ca. 0.8 V range at low (< 100 pA) current. A theoretical model, based upon first principles electronic structure calculations and quantum mechanical wavepacket simulations, traces these observations to multi-mode dynamics triggered by a transition into a cationic resonance. The model is generalized to provide understanding of, and suggest a means of control over, the behaviour of different classes of organic adsorbates under tunneling current.     

Different surface chemistries of water on Ru[0001]: from monomer adsorption to partially dissociated bilayers

Density functional theory has been used to perform a comparative theoretical study of the adsorption and dissociation of H(2)O monomers and icelike bilayers on Ru[0001]. H(2)O monomers bind preferentially at atop sites with an adsorption energy of approximately 0.4 eV/H(2)O. The main bonding interaction is through the H(2)O 1b(1) molecular orbital which mixes with Ru d(z)2 states. The lower-lying set of H(2)O molecules in an intact H(2)O bilayer bond in a similar fashion; the high-lying H(2)O molecules, however, do not bond directly with the surface, rather they are held in place through H bonding. The H(2)O adsorption energy in intact bilayers is approximately 0.6 eV/H(2)O and we estimate that H bonding accounts for approximately 70% of this. In agreement with Feibelman (Science 2002, 295, 99) we find that a partially dissociated OH + H(2)O overlayer is energetically favored over pure intact H(2)O bilayers on the surface. The barrier for the dissociation of a chemisorbed H(2)O monomer is 0.8 eV, whereas the barrier to dissociate a H(2)O incorporated in a bilayer is just 0.5 eV.     

Molecular dynamics simulations of the oxidation of aluminum nanoparticles

The oxidation of aluminum nanoparticles is studied with classical molecular dynamics and the Streitz-Mintmire (Streitz, F. H.; Mintmire, J. W. Phys. Rev. B 1994, 50, 11996) electrostatic plus (ES+) potential that allows for the variation of electrostatic charge on all atoms in the simulation. The structure and charge distributions of bulk crystalline alpha-Al(2)O(3), a surface slab of alpha-Al(2)O(3) with an exposed (0001) basal plane, and an isolated Al(2)O(3) nanoparticle are studied. Constant NVT simulations of the oxidation of aluminum nanoparticles are also performed with different oxygen exposures. The calculations simulate a thermostated one-time exposure of an aluminum nanoparticle to different numbers of surface oxygen atoms. In the first set of oxidation studies, the overall approximate ratios of Al to O in the nanoparticle are 1:1 and 2:1. The nanoparticles are annealed to 3000 K and are then cooled to 500, 1000, or 1500 K. The atomic kinetic energy is scaled during the simulation to maintain the desired temperature. The structure and charge distributions in the oxidized nanoparticles differ from each other and from those of the bulk Al(2)O(3) phases. In the Al(1)O(1) simulation, an oxide shell forms that stabilizes the shape of the particle, and thus the original structure of the nanoparticle is approximately retained. In the case of Al(1)O(0.5), there is insufficient oxygen to form a complete oxide shell, and the oxidation results in particles of irregular shapes and rough surfaces. The particle surface is rough, and the nanoparticle is deformed.     

A comparison of Hartree-Fock and exact diagonalization solutions for a model two-electron system

We compare the restricted (RHF) and unrestricted (UHF) Hartree-Fock solutions with the exact configuration interaction (CI) solutions for the model problem of two interacting electrons confined within an infinite spherical potential of radius R. An investigation of the ground state energy, electron density, and a population analysis of the wave functions reveals that the UHF solution compares favorably with the CI one in both the small and large R limits. The Coulson-Fischer transition (the point at which the RHF and UHF solutions are no longer degenerate) occurs at an r(s) identical with R/2(1/3) approximately 6 a.u., close to the crossover r(s) where the exact CI density acquires a minimum at the sphere center; this behavior captures the onset of Wigner molecule formation. In this regime, however, the HF densities and energies are not quantitatively accurate when compared to the CI ones. This failure is further quantified by computing Ec/E to determine the ability of each method at capturing the exact correlation energy; we conclude that the UHF solutions can be reasonably accurate at both high and low densities, but not at intermediate r(s).     

Theoretical predictions of the initial decomposition steps of dimethylnitramine

The structures and energies of the reactants, products, and transition states of the initial steps in the gas-phase decomposition of dimethylnitramine (DMNA) have been determined by quantum chemical calculations at the B3LYP density-functional theory, MP2, and G2 levels. The pathways considered are NO2 elimination, HONO elimination, and nitro-nitrite rearrangement. The NO2 elimination is predicted to be the main channel of the gas-phase decomposition of DMNA in accord with experiment. The values of the Arrhenius parameters, log A=16.6+/-0.5 and Ea=40.0+/-0.6 kcal/mol, for the N-NO2 bond-fission reaction were obtained using a canonical variational theory with B3LYP energies and frequencies. The HONO-elimination channel has the next lowest activation energy of 44.7+/-0.5 kcal/mol (log A=13.6+/-0.5) and is characterized by a five-member transition-state configuration in which a hydrogen atom from one of the methyl groups is transferred to an oxygen atom of NO2. Tunneling contributions to the rate of this reaction have been estimated. The nitro-nitrite rearrangement reaction occurs via a transition state in which both oxygen atoms of NO2 are loosely bound to the central nitrogen atom, for which Rice-Ramsperger-Kassel-Marcus theory predicts log A=14.4+/-0.6 and Ea=54.1+/-0.8 kcal/mol.     

Magnetically recoverable AlFe/Te nanocomposite as a new catalyst for the facile esterification reaction under neat conditions

In this work, a new Fe₃O₄/AlFe/Te nanocomposite was synthesized by a one‐step sol–gel method. The Fe₃O₄ magnetic nanoparticles (MNPs) were prepared and then mixed with aluminum telluride (Al₂Te₃) in an alkali medium to produce the desired catalyst. After characterization of the Fe₃O₄/AlFe/Te nanocomposite by SEM, TEM, EDS, XRD, and ICP analyses, it was used in the esterification reaction. This heterogeneous catalyst showed high catalytic activity in the esterification of commercially available carboxylic acids with various alcohols to produce the desired esters at high conversions under neat conditions. The Fe₃O₄/AlFe/Te nanocomposites were separated from the reaction mixture via an external magnet and re‐used 8 times without significant loss of catalytic activity.     

Antimicrobial and wound healing activities of electrospun nanofibers based on functionalized carbohydrates and proteins

The anti-adhesion, anti-growth and the anti-penetration of bacteria, specifically multidrug-resistant bacteria, should be taken into consideration when designing promising wound dressings for infected wounds such as diabetic foot ulcers. Wound dressings composed of natural polymeric nanofibers such as functionalized cellulose, chitosan, alginate, hyaluronic acid, dextrin and cyclodextrin with appropriate antimicrobial and skin reconstruction properties are suitable alternatives that can accelerate wound healing and remove microbial infections. For instance, to improve the release profile of antibacterial agents such as metal nanoparticles and antibiotics, water-soluble polymers like polyethylene oxide and polyvinylpyrrolidone may be incorporated into polymeric nanofiber scaffolds. This review, therefore, addresses the current status and future challenges of antibacterial activities of nanofiber scaffolds composed of some of the natural occurring polymers.

     

Counterion influence on the N–I–N halogen bond

A detailed investigation of the influence of counterions on the [N–I–N]⁺ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]⁺ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(i) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(i) complexes are converted into multi-coordinate geometries with strong Ag–O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by ¹⁵N NMR and DFT computation. This suggests that the [N–I–N]⁺ halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character.