408 research outputs found

### Beyond the RPA on the cheap: improved correlation energies with the efficient "Radial Exchange Hole" kernel

The "ACFD-RPA" correlation energy functional has been widely applied to a
variety of systems to successfully predict energy differences, and less
successfully predict absolute correlation energies. Here we present a
parameter-free exchange-correlation kernel that systematically improves
absolute correlation energies, while maintaining most of the good numerical
properties that make the ACFD-RPA numerically tractable. The "RXH" kernel is
constructed to approximate the true exchange kernel via a carefully weighted,
easily computable radial averaging. Correlation energy errors of atoms with two
to eighteen electrons show a thirteenfold improvement over the RPA and a
threefold improvement over the related "PGG" kernel, for a mean absolute error
of 13mHa or 5%. The average error is small compared to all but the most
difficult to evaluate kernels. van der Waals $C_6$ coefficients are less well
predicted, but still show improvements on the RPA, especially for highly
polarisable Li and Na

### Efficient, long-range correlation from occupied wavefunctions only

We use continuum mechanics [Tao \emph{et al}, PRL{\bf 103},086401] to
approximate the dynamic density response of interacting many-electron systems.
Thence we develop a numerically efficient exchange-correlation energy
functional based on the Random Phase Approximation (dRPA). The resulting
binding energy curve $E(D)$ for thin parallel metal slabs at separation $D$
better agrees with full dRPA calculations than does the Local Density
Approximation. We also reproduce the correct non-retarded van der Waals (vdW)
power law E(D)\aeq -C_{5/2}D^{-5/2} as $D\to\infty$, unlike most vdW
functionals.Comment: 4 pages, 1 figur

### The flexible nature of exchange, correlation and Hartree physics: resolving "delocalization" errors in a 'correlation free' density functional

By exploiting freedoms in the definitions of 'correlation', 'exchange' and
'Hartree' physics in ensemble systems we better generalise the notion of 'exact
exchange' (EXX) to systems with fractional occupations functions of the
frontier orbitals, arising in the dissociation limit of some molecules. We
introduce the Linear EXX ("LEXX") theory whose pair distribution and energy are
explicitly \emph{piecewise linear} in the occupations $f^{\sigma}_{i}$. {\hi}We
provide explicit expressions for these functions for frontier $s$ and $p$
shells. Used in an optimised effective potential (OEP) approach it yields
energies bounded by the piecewise linear 'ensemble EXX' (EEXX) energy and
standard fractional optimised EXX energy: $E^{EEXX}\leq E^{LEXX} \leq E^{EXX}$.
Analysis of the LEXX explains the success of standard OEP methods for diatoms
at large spacing, and why they can fail when both spins are allowed to be
non-integer so that "ghost" Hartree interactions appear between \emph{opposite}
spin electrons in the usual formula. The energy $E^{LEXX}$ contains a
cancellation term for the spin ghost case. It is evaluated for H, Li and Na
fractional ions with clear derivative discontinuities for all cases. The
$p$-shell form reproduces accurate correlation-free energies of B-F and Al-Cl.
We further test LEXX plus correlation energy calculations on fractional ions of
C and F and again shows both derivative discontinuities and good agreement with
exact results

### Dispersion corrections in graphenic systems: a simple and effective model of binding

We combine high-level theoretical and \emph{ab initio} understanding of
graphite to develop a simple, parametrised force-field model of interlayer
binding in graphite, including the difficult non-pairwise-additive
coupled-fluctuation dispersion interactions. The model is given as a simple
additive correction to standard density functional theory (DFT) calculations,
of form $\Delta U(D)=f(D)[U^{vdW}(D)-U^{DFT}(D)]$ where $D$ is the interlayer
distance. The functions are parametrised by matching contact properties, and
long-range dispersion to known values, and the model is found to accurately
match high-level \emph{ab initio} results for graphite across a wide range of
$D$ values. We employ the correction on the difficult bigraphene binding and
graphite exfoliation problems, as well as lithium intercalated graphite
LiC$_6$. We predict the binding energy of bigraphene to be 0.27 J/m^2, and the
exfoliation energy of graphite to be 0.31 J/m^2, respectively slightly less and
slightly more than the bulk layer binding energy 0.295 J/m^2/layer. Material
properties of LiC$_6$ are found to be essentially unchanged compared to the
local density approximation. This is appropriate in view of the relative
unimportance of dispersion interactions for LiC$_6$ layer binding

### How many-body effects modify the van der Waals interaction between graphene sheets

Undoped graphene (Gr) sheets at low temperatures are known, via Random Phase
Approximation (RPA) calculations, to exhibit unusual van der Waals (vdW)
forces. Here we show that graphene is the first known system where effects
beyond the RPA make qualitative changes to the vdW force. For large
separations, $D \gtrsim 10$nm where only the $\pi_z$ vdW forces remain, we find
the Gr-Gr vdW interaction is substantially reduced from the RPA prediction. Its
$D$ dependence is very sensitive to the form of the long-wavelength many-body
enhancement of the velocity of the massless Dirac fermions, and may provide
independent confirmation of the latter via direct force measurements.Comment: 3 Figures: PACS 73.22.Pr, 71.10.Pm, 61.48.Gh, 34.20.C

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