29 research outputs found
M{\o}ller-Plesset and density-fixed adiabatic connections for a model diatomic system at different correlation regimes
In recent years, Adiabatic Connection Interpolations developed within Density
Functional Theory (DFT) have been found to provide satisfactory performances in
the calculation of interaction energies when used with Hartree-Fock (HF)
ingredients. The physical and mathematical reasons for such unanticipated
performance have been clarified, to some extent, by studying the
strong-interaction limit of the M\o ller-Plesset (MP) adiabatic connection. In
this work, we calculate both the MP and the DFT adiabatic connection (AC)
integrand for the asymmetric Hubbard dimer, which allows for a systematic
investigation at different correlation regimes by varying two simple parameters
in the Hamiltonian: the external potential, , and the interaction
strength, . Noticeably, we find that, while the DFT AC integrand appears to
be convex in the full parameter space, the MP integrand may change curvature
twice. Furthermore, we discuss different aspects of the second-order expansion
of the correlation energy in each adiabatic connection and we demonstrate that
the derivative of the -dependent density in the MP adiabatic
connection at (i.e., at the HF density) is zero. Concerning the
strong-interaction limit of both adiabatic connections, we show that while, for
a given density, the asymptotic value of the MP adiabatic connection,
, is lower (or equal) than its DFT analogue,
, this is not always the case for a given external
potential
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Approaching periodic systems in ensemble density functional theory via finite one-dimensional models
Abstract:
Ensemble Density Functional Theory (EDFT) is a generalization of ground-state Density Functional Theory (GS DFT), which is based on an exact formal theory of finite collections of a system's ground and excited states. EDFT in various forms has been shown to improve the accuracy of calculated energy level differences in isolated model systems, atoms, and molecules, but it is not yet clear how EDFT could be used to calculate band gaps for periodic systems. We extend the application of EDFT toward periodic systems by estimating the thermodynamic limit with increasingly large finite one-dimensional "particle in a box" systems, which approach the uniform electron gas (UEG). Using ensemble-generalized Hartree and Local Spin Density Approximation (LSDA) exchange-correlation functionals, we find that corrections go to zero in the infinite limit, as expected for a metallic system. However, there is a correction to the effective mass, with results comparable to other calculations on 1D, 2D, and 3D UEGs, which indicates promise for non-trivial results from EDFT on periodic systems
Excitations and benchmark ensemble density functional theory for two electrons
A new method for extracting ensemble Kohn-Sham potentials from accurate
excited state densities is applied to a variety of two electron systems,
exploring the behavior of exact ensemble density functional theory. The issue
of separating the Hartree energy and the choice of degenerate eigenstates is
explored. A new approximation, spin eigenstate Hartree-exchange (SEHX), is
derived. Exact conditions that are proven include the signs of the correlation
energy components, the virial theorem for both exchange and correlation, and
the asymptotic behavior of the potential for small weights of the excited
states. Many energy components are given as a function of the weights for two
electrons in a one-dimensional flat box, in a box with a large barrier to
create charge transfer excitations, in a three-dimensional harmonic well
(Hooke's atom), and for the He atom singlet-triplet ensemble,
singlet-triplet-singlet ensemble, and triplet bi-ensemble.Comment: 15 pages, supplemental material pd