10,603 research outputs found
Fixed-node diffusion Monte Carlo study of the structures of m-benzyne
Diffusion Monte Carlo (DMC) calculations are performed on the monocyclic and
bicyclic forms of m-benzyne, which are the equilibrium structures at the
CCSD(T) and CCSD levels of coupled cluster theory. We employed
multi-configuration self-consistent field trial wave functions which are
constructed from a carefully selected 8-electrons-in-8-orbitals complete active
space [CAS(8,8)], with CSF coefficients that are reoptimized in the presence of
a Jastrow factor. The DMC calculations show that the monocyclic structure is
lower in energy than the bicyclic structure by 1.9(2) kcal/mole, in excellent
agreement with the best coupled cluster results.Comment: 5 pages, 2 figures. to be published in JC
Nonempirical Density Functionals Investigated for Jellium: Spin-Polarized Surfaces, Spherical Clusters, and Bulk Linear Response
Earlier tests show that the Tao-Perdew-Staroverov-Scuseria (TPSS)
nonempirical meta-generalized gradient approximation (meta-GGA) for the
exchange-correlation energy yields more accurate surface energies than the
local spin density (LSD) approximation for spin-unpolarized jellium. In this
study, work functions and surface energies of a jellium metal in the presence
of ``internal'' and external magnetic fields are calculated with LSD,
Perdew-Burke-Ernzerhof (PBE) GGA, and TPSS meta-GGA and its predecessor, the
nearly nonempirical Perdew-Kurth-Zupan-Blaha (PKZB) meta-GGA, using
self-consistent LSD orbitals and densities. The results show that: (i) For
normal bulk densities, the surface correlation energy is the same in TPSS as in
PBE, as it should be since TPSS strives to represent a self-correlation
correction to PBE; (ii) Normal surface density profiles can be scaled uniformly
to the low-density or strong-interaction limit, and TPSS provides an estimate
for that limit that is consistent with (but probably more accurate than) other
estimates; (iii) For both normal and low densities, TPSS provides the same
description of surface magnetism as PBE, suggesting that these approximations
may be generally equivalent for magnetism. The energies of jellium spheres with
up to 106 electrons are calculated using density functionals and compared to
those obtained with Diffusion Quantum Monte Carlo data, including our estimate
for the fixed-node correction. Finally we calculate the linear response of bulk
jellium using these density functionals, and find that not only LSD but also
PBE GGA and TPSS meta-GGA yield a linear-response in good agreement with that
of the Quantum Monte Carlo method, for wavevectors of the perturbing external
potential up to twice the Fermi wavevector.Comment: 14 pages, 9 figure
A natural orbital functional for the many-electron problem
The exchange-correlation energy in Kohn-Sham density functional theory is
expressed as a functional of the electronic density and the Kohn-Sham orbitals.
An alternative to Kohn-Sham theory is to express the energy as a functional of
the reduced first-order density matrix or equivalently the natural orbitals. In
the former approach the unknown part of the functional contains both a kinetic
and a potential contribution whereas in the latter approach it contains only a
potential energy and consequently has simpler scaling properties. We present an
approximate, simple and parameter-free functional of the natural orbitals,
based solely on scaling arguments and the near satisfaction of a sum rule. Our
tests on atoms show that it yields on average more accurate energies and charge
densities than the Hartree Fock method, the local density approximation and the
generalized gradient approximations
Ab initio pseudopotential study of Fe, Co, and Ni employing the spin-polarized LAPW approach
The ground-state properties of Fe, Co, and Ni are studied with the
linear-augmented-plane-wave (LAPW) method and norm-conserving pseudopotentials.
The calculated lattice constant, bulk modulus, and magnetic moment with both
the local-spin-density approximation (LSDA) and the generalized gradient
approximation (GGA) are in good agreement with those of all-electron
calculations, respectively. The GGA results show a substantial improvement over
the LSDA results, i.e., better agreement with experiment. The accurate
treatment of the nonlinear core-valence exchange and correlation interaction is
found to be essential for the determination of the magnetic properties of 3d
transition metals. The present study demonstrates the successful application of
the LAPW pseudopotential approach to the calculation of ground-state properties
of magnetic 3d transition metals.Comment: RevTeX, 14 pages, 2 figures in uufiles for
Assessment of density-functional approximations: Long-range correlations and self-interaction effects
The complex nature of electron-electron correlations is made manifest in the very simple but nontrivial problem of two electrons confined within a sphere. The description of highly nonlocal correlation and self-interaction effects by widely used local and semilocal exchange-correlation energy density functionals is shown to be unsatisfactory in most cases. Even the best such functionals exhibit significant errors in the Kohn-Sham potentials and density profiles
Effects of 3-d and 4-d-transition metal substitutional impurities on the electronic properties of CrO2
We present first-principles based density functional theory calculations of
the electronic and magnetic structure of CrO2 with 3d (Ti through Cu) and 4d
(Zr through Ag) substitutional impurities. We find that the half-metallicity of
CrO2 remains intact for all of the calculated substitutions. We also observe
two periodic trends as a function of the number of valence electrons: if the
substituted atom has six or fewer valence electrons (Ti-Cr or Zr-Mo), the
number of down spin electrons associated with the impurity ion is zero,
resulting in ferromagnetic (FM) alignment of the impurity magnetic moment with
the magnetization of the CrO2 host. For substituent atoms with eight to ten
(Fe-Ni or Ru-Pd with the exception of Ni), the number of down spin electrons
contributed by the impurity ion remains fixed at three as the number
contributed to the majority increases from one to three resulting in
antiferromagnetic (AFM) alignment between impurity moment and host
magnetization. The origin of this variation is the grouping of the impurity
states into 3 states with approximate "t2g" symmetry and 2 states with
approximate "eg" symmetry. Ni is an exception to the rule because a
Jahn-Teller-like distortion causes a splitting of the Ni eg states. For Mn and
Tc, which have 8 valence electrons, the zero down spin and 3 down spin
configurations are very close in energy. For Cu and Ag atoms, which have 11
valence electrons, the energy is minimized when the substituent ion contributes
5 Abstract down-spin electrons. We find that the interatomic exchange
interactions are reduced for all substitutions except for the case of Fe for
which a modest enhancement is calculated for interactions along certain
crystallographic directions.Comment: 26 pages, 10 figures, 2 table
Transport in Molecular Junctions with Different Metallic Contacts
Ab initio calculations of phenyl dithiol connected to Au, Ag, Pd, and Pt
electrodes are performed using non-equilibrium Green's functions and density
functional theory. For each metal, the properties of the molecular junction are
considered both in equilibrium and under bias. In particular, we consider in
detail charge transfer, changes in the electrostatic potential, and their
subsequent effects on the IV curves through the junctions. Gold is typically
used in molecular junctions because it forms strong chemical bonds with sulfur.
We find however that Pt and Pd make better electrical contacts than Au. The
zero-bias conductance is found to be greatest for Pt, followed by Pd, Au, and
then Ag
Density-relaxation part of the self energy
A comment is made on the large-cluster limit of the self-energy correction for the quasiparticle energy gap in silicon clusters presented by Serdar Ogut, James R. Chelikowsky and Steven G. Louie in Phys. Rev. Lett. 79, 1770 (1997)
Exact condition on the Kohn-Sham kinetic energy, and modern parametrization of the Thomas-Fermi density
We study the asymptotic expansion of the neutral-atom energy as the atomic
number Z goes to infinity, presenting a new method to extract the coefficients
from oscillating numerical data. We find that recovery of the correct expansion
is an exact condition on the Kohn-Sham kinetic energy that is important for the
accuracy of approximate kinetic energy functionals for atoms, molecules and
solids, when evaluated on a Kohn-Sham density. For example, this determines the
small gradient limit of any generalized gradient approximation, and conflicts
somewhat with the standard gradient expansion. Tests are performed on atoms,
molecules, and jellium clusters. We also give a modern, highly accurate
parametrization of the Thomas-Fermi density of neutral atoms.Comment: 10 pages, 9 figures, submitted at JC
Slabs of stabilized jellium: Quantum-size and self-compression effects
We examine thin films of two simple metals (aluminum and lithium) in the
stabilized jellium model, a modification of the regular jellium model in which
a constant potential is added inside the metal to stabilize the system for a
given background density. We investigate quantum-size effects on the surface
energy and the work function. For a given film thickness we also evaluate the
density yielding energy stability, which is found to be slightly higher than
the equilibrium density of the bulk system and to approach this value in the
limit of thick slabs. A comparison of our self-consistent calculations with the
predictions of the liquid-drop model shows the validity of this model.Comment: 7 pages, 6 figures, to appear in Phys. Rev.
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