663 research outputs found
Stability and aromaticity of nH2@B12N12 (n=1â12) clusters
Standard ab initio and density functional calculations are carried out to determine the structure, stability, and reactivity of B12N12 clusters with hydrogen doping. To lend additional support, conceptual DFT-based reactivity descriptors and the associated electronic structure principles are also used. Related cage aromaticity of this B12N12 and nH2@B12N12 are analyzed through the nucleus independent chemical shift values
Harmonically trapped jellium
We discuss the model of a -dimensional confined electron gas in which the
particles are trapped by a harmonic potential. In particular, we study the
non-interacting kinetic and exchange energies of finite-size inhomogeneous
systems, and compare the resulting Thomas-Fermi and Dirac coefficients with
various uniform electron gas paradigms. We show that, in the thermodynamic
limit, the properties of this model are identical to those of the
-dimensional Fermi gas.Comment: 6 pages, 2 figures, 1 table, invited paper for Peter Taylor's 60th
anniversary, submitted to Molecular Physic
Excited states of spherium
We report analytic solutions of a recently discovered quasi-exactly solvable
model consisting of two electrons, interacting {\em via} a Coulomb potential,
but restricted to remain on the surface of a -dimensional sphere.
Polynomial solutions are found for the ground state, and for some higher
() states. Kato cusp conditions and interdimensional degeneracies are
discussed.Comment: 6 pages, 2 figures, to appear in Mol. Phy
Computational Complexity of interacting electrons and fundamental limitations of Density Functional Theory
One of the central problems in quantum mechanics is to determine the ground
state properties of a system of electrons interacting via the Coulomb
potential. Since its introduction by Hohenberg, Kohn, and Sham, Density
Functional Theory (DFT) has become the most widely used and successful method
for simulating systems of interacting electrons, making their original work one
of the most cited in physics. In this letter, we show that the field of
computational complexity imposes fundamental limitations on DFT, as an
efficient description of the associated universal functional would allow to
solve any problem in the class QMA (the quantum version of NP) and thus
particularly any problem in NP in polynomial time. This follows from the fact
that finding the ground state energy of the Hubbard model in an external
magnetic field is a hard problem even for a quantum computer, while given the
universal functional it can be computed efficiently using DFT. This provides a
clear illustration how the field of quantum computing is useful even if quantum
computers would never be built.Comment: 8 pages, 3 figures. v2: Version accepted at Nature Physics; differs
significantly from v1 (including new title). Includes an extra appendix (not
contained in the journal version) on the NP-completeness of Hartree-Fock,
which is taken from v
Using the local density approximation and the LYP, BLYP, and B3LYP functionals within Reference--State One--Particle Density--Matrix Theory
For closed-shell systems, the local density approximation (LDA) and the LYP,
BLYP, and B3LYP functionals are shown to be compatible with reference-state
one-particle density-matrix theory, where this recently introduced formalism is
based on Brueckner-orbital theory and an energy functional that includes exact
exchange and a non-universal correlation-energy functional. The method is
demonstrated to reduce to a density functional theory when the
exchange-correlation energy-functional has a simplified form, i.e., its
integrand contains only the coordinates of two electron, say r1 and r2, and it
has a Dirac delta function -- delta(r1 - r2) -- as a factor. Since Brueckner
and Hartree--Fock orbitals are often very similar, any local exchange
functional that works well with Hartree--Fock theory is a reasonable
approximation with reference-state one-particle density-matrix theory. The LDA
approximation is also a reasonable approximation. However, the Colle--Salvetti
correlation-energy functional, and the LYP variant, are not ideal for the
method, since these are universal functionals. Nevertheless, they appear to
provide reasonable approximations. The B3LYP functional is derived using a
linear combination of two functionals: One is the BLYP functional; the other
uses exact exchange and a correlation-energy functional from the LDA.Comment: 26 Pages, 0 figures, RevTeX 4, Submitted to Mol. Phy
Classical kinetic energy, quantum fluctuation terms and kinetic-energy functionals
We employ a recently formulated dequantization procedure to obtain an exact
expression for the kinetic energy which is applicable to all kinetic-energy
functionals. We express the kinetic energy of an N-electron system as the sum
of an N-electron classical kinetic energy and an N-electron purely quantum
kinetic energy arising from the quantum fluctuations that turn the classical
momentum into the quantum momentum. This leads to an interesting analogy with
Nelson's stochastic approach to quantum mechanics, which we use to conceptually
clarify the physical nature of part of the kinetic-energy functional in terms
of statistical fluctuations and in direct correspondence with Fisher
Information Theory. We show that the N-electron purely quantum kinetic energy
can be written as the sum of the (one-electron) Weizsacker term and an
(N-1)-electron kinetic correlation term. We further show that the Weizsacker
term results from local fluctuations while the kinetic correlation term results
from the nonlocal fluctuations. For one-electron orbitals (where kinetic
correlation is neglected) we obtain an exact (albeit impractical) expression
for the noninteracting kinetic energy as the sum of the classical kinetic
energy and the Weizsacker term. The classical kinetic energy is seen to be
explicitly dependent on the electron phase and this has implications for the
development of accurate orbital-free kinetic-energy functionals. Also, there is
a direct connection between the classical kinetic energy and the angular
momentum and, across a row of the periodic table, the classical kinetic energy
component of the noninteracting kinetic energy generally increases as Z
increases.Comment: 10 pages, 1 figure. To appear in Theor Chem Ac
Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles
ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence
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