2,788 research outputs found
The limitations of Slater's element-dependent exchange functional from analytic density functional theory
Our recent formulation of the analytic and variational Slater-Roothaan (SR)
method, which uses Gaussian basis sets to variationally express the molecular
orbitals, electron density and the one body effective potential of density
functional theory, is reviewed. Variational fitting can be extended to the
resolution of identity method,where variationality then refers to the error in
each two electron integral and not to the total energy. It is proposed that the
appropriate fitting functions be charge neutral and that all ab initio energies
be evaluated using two-center fits of the two-electron integrals. The SR method
has its root in the Slater's Xalpha method and permits an arbitrary scaling of
the Slater-Gaspar-Kohn-Sham exchange-correlation potential around each atom in
the system. Of several ways of choosing the scaling factors (Slater's exchange
parameters), two most obvious are the Hartree-Fock (HF), alpha_HF, values and
the exact atomic, alpha_EA, values. The performance of this simple analytic
model with both sets for atomization energies of G2 set of 148 molecules is
better than the local density approximation or the HF theory, although the
errors in atomization energy are larger than the target chemical accuracy.
To improve peformance for atomization energies, the SR method is
reparametrized to give atomization energies of 148 molecules to be comparbale
to those obtained by one of the most widely used generalized gradient
approximations. The mean absolute error in ionization potentials of 49 atoms
and molecules is about 0.5 eV and that in bond distances of 27 molecules is
about 0.02 Angstrom. The overall good performance of the computationally
efficient SR method using any reasonable set of alpha values makes it a
promising method for study of large systems.Comment: 33 pages, Uses RevTex, to appear in The Journal of Chemical Physic
Accurate molecular energies by extrapolation of atomic energies using an analytic quantum mechanical model
Using a new analytic quantum mechanical method based on Slater's Xalpha
method, we show that a fairly accurate estimate of the total energy of a
molecule can be obtained from the exact energies of its constituent atoms. The
mean absolute error in the total energies thus determined for the G2 set of 56
molecules is about 16 kcal/mol, comparable to or better than some popular pure
and hybrid density functional models.Comment: 5 pages, REVTE
Evidence from K2 for rapid rotation in the descendant of an intermediate-mass star
Using patterns in the oscillation frequencies of a white dwarf observed by
K2, we have measured the fastest rotation rate, 1.13(02) hr, of any isolated
pulsating white dwarf known to date. Balmer-line fits to follow-up spectroscopy
from the SOAR telescope show that the star (SDSSJ0837+1856, EPIC 211914185) is
a 13,590(340) K, 0.87(03) solar-mass white dwarf. This is the highest mass
measured for any pulsating white dwarf with known rotation, suggesting a
possible link between high mass and fast rotation. If it is the product of
single-star evolution, its progenitor was a roughly 4.0 solar-mass
main-sequence B star; we know very little about the angular momentum evolution
of such intermediate-mass stars. We explore the possibility that this rapidly
rotating white dwarf is the byproduct of a binary merger, which we conclude is
unlikely given the pulsation periods observed.Comment: 5 pages, 4 figure, 1 table; accepted for publication in The
Astrophysical Journal Letter
A Nonpolar Blueberry Fraction Blunts NADPH Oxidase Activation in Neuronal Cells Exposed to Tumor Necrosis Factor-α
Inflammation and oxidative stress are key to the progressive neuronal degeneration common to chronic pathologies, traumatic injuries, and aging processes in the CNS. The proinflammatory cytokine tumor necrosis factor-alpha (TNF-α) orchestrates cellular stress by stimulating the production and release of neurotoxic mediators including reactive oxygen species (ROS). NADPH oxidases (NOX), ubiquitously expressed in all cells, have recently emerged as pivotal ROS sources in aging and disease. We demonstrated the presence of potent NOX inhibitors in wild Alaska bog blueberries partitioning discretely into a nonpolar fraction with minimal antioxidant capacity and largely devoid of polyphenols. Incubation of SH-SY5Y human neuroblastoma cells with nonpolar blueberry fractions obstructed the coalescing of lipid rafts into large domains disrupting NOX assembly therein and abolishing ROS production characteristic for TNF-α exposure. These findings illuminate nutrition-derived lipid raft modulation as a novel therapeutic approach to blunt inflammatory and oxidative stress in the aging or diseased CNS
Direct Minimization Generating Electronic States with Proper Occupation Numbers
We carry out the direct minimization of the energy functional proposed by
Mauri, Galli and Car to derive the correct self-consistent ground state with
fractional occupation numbers for a system degenerating at the Fermi level. As
a consequence, this approach enables us to determine the electronic structure
of metallic systems to a high degree of accuracy without the aid of level
broadening of the Fermi-distribution function. The efficiency of the method is
illustrated by calculating the ground-state energy of C and Si
molecules and the W(110) surface to which a tungsten adatom is adsorbed.Comment: 4 pages, 4 figure
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Magnetic relaxation in highly anisotropic systems
Using the Mori formalism, a general theory is developed for the calculation of paramagnetic relaxation effects in a general crystal field doublet. For systems with extreme magnetic anisotropy, the relaxation rates show a strong angular dependence, being severely peaked in a direction perpendicular to the magnetic easy axis. Application to the RRh/sub 4/B/sub 4/ (R = rare-earth) compounds is discussed. 5 refs
Fourier analyses of commensurability oscillations in Fibonacci lateral superlattices
Magnetotransport measurements have been performed on Fibonacci lateral
superlattices (FLSLs) -- two-dimensional electron gases subjected to a weak
potential modulation arranged in the Fibonacci sequence, LSLLSLS..., with
L/S=tau (the golden ratio). Complicated commensurability oscillation (CO) is
observed, which can be accounted for as a superposition of a series of COs each
arising from a sinusoidal modulation representing the characteristic length
scale of one of the self-similar generations in the Fibonacci sequence.
Individual CO components can be separated out from the magnetoresistance trace
by performing a numerical Fourier band-pass filter. From the analysis of the
amplitude of a single-component CO thus extracted, the magnitude of the
corresponding Fourier component in the potential modulation can be evaluated.
By examining all the Fourier contents observed in the magnetoresistance trace,
the profile of the modulated potential seen by the electrons can be
reconstructed with some remaining ambiguity about the interrelation of the
phase between different components.Comment: 11 pages, 10 figures, added references in Introduction, minor
revision
Quantitative analysis of regulatory flexibility under changing environmental conditions
The circadian clock controls 24-h rhythms in many biological processes, allowing appropriate timing of biological rhythms relative to dawn and dusk. Known clock circuits include multiple, interlocked feedback loops. Theory suggested that multiple loops contribute the flexibility for molecular rhythms to track multiple phases of the external cycle. Clear dawn- and dusk-tracking rhythms illustrate the flexibility of timing in Ipomoea nil. Molecular clock components in Arabidopsis thaliana showed complex, photoperiod-dependent regulation, which was analysed by comparison with three contrasting models. A simple, quantitative measure, Dusk Sensitivity, was introduced to compare the behaviour of clock models with varying loop complexity. Evening-expressed clock genes showed photoperiod-dependent dusk sensitivity, as predicted by the three-loop model, whereas the one- and two-loop models tracked dawn and dusk, respectively. Output genes for starch degradation achieved dusk-tracking expression through light regulation, rather than a dusk-tracking rhythm. Model analysis predicted which biochemical processes could be manipulated to extend dusk tracking. Our results reveal how an operating principle of biological regulators applies specifically to the plant circadian clock
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