57 research outputs found
Electronic levels and electrical response of periodic molecular structures from plane-wave orbital-dependent calculations
Plane-wave electronic-structure predictions based upon orbital-dependent
density-functional theory (OD-DFT) approximations, such as hybrid
density-functional methods and self-interaction density-functional corrections,
are severely affected by computational inaccuracies in evaluating electron
interactions in the plane-wave representation. These errors arise from
divergence singularities in the plane-wave summation of electrostatic and
exchange interaction contributions. Auxiliary-function corrections are
reciprocal-space countercharge corrections that cancel plane-wave singularities
through the addition of an auxiliary function to the point-charge electrostatic
kernel that enters into the expression of interaction terms. At variance with
real-space countercharge corrections that are employed in the context of
density-functional theory (DFT), reciprocal-space corrections are
computationally inexpensive, making them suited to more demanding OD-DFT
calculations. Nevertheless, there exists much freedom in the choice of
auxiliary functions and various definitions result in different levels of
performance in eliminating plane-wave inaccuracies. In this work, we derive
exact point-charge auxiliary functions for the description of molecular
structures of arbitrary translational symmetry, including the yet unaddressed
one-dimensional case. In addition, we provide a critical assessment of
different reciprocal-space countercharge corrections and demonstrate the
improved accuracy of point-charge auxiliary functions in predicting the
electronic levels and electrical response of conjugated polymers from
plane-wave OD-DFT calculations.Comment: 11 pages, 7 figure
Revised self-consistent continuum solvation in electronic-structure calculations
The solvation model proposed by Fattebert and Gygi [Journal of Computational
Chemistry 23, 662 (2002)] and Scherlis et al. [Journal of Chemical Physics 124,
074103 (2006)] is reformulated, overcoming some of the numerical limitations
encountered and extending its range of applicability. We first recast the
problem in terms of induced polarization charges that act as a direct mapping
of the self-consistent continuum dielectric; this allows to define a functional
form for the dielectric that is well behaved both in the high-density region of
the nuclear charges and in the low-density region where the electronic
wavefunctions decay into the solvent. Second, we outline an iterative procedure
to solve the Poisson equation for the quantum fragment embedded in the solvent
that does not require multi-grid algorithms, is trivially parallel, and can be
applied to any Bravais crystallographic system. Last, we capture some of the
non-electrostatic or cavitation terms via a combined use of the quantum volume
and quantum surface [Physical Review Letters 94, 145501 (2005)] of the solute.
The resulting self-consistent continuum solvation (SCCS) model provides a very
effective and compact fit of computational and experimental data, whereby the
static dielectric constant of the solvent and one parameter allow to fit the
electrostatic energy provided by the PCM model with a mean absolute error of
0.3 kcal/mol on a set of 240 neutral solutes. Two parameters allow to fit
experimental solvation energies on the same set with a mean absolute error of
1.3 kcal/mol. A detailed analysis of these results, broken down along different
classes of chemical compounds, shows that several classes of organic compounds
display very high accuracy, with solvation energies in error of 0.3-0.4
kcal/mol, whereby larger discrepancies are mostly limited to self-dissociating
species and strong hydrogen-bond forming compounds.Comment: The following article has been accepted by The Journal of Chemical
Physics. After it is published, it will be found at
http://link.aip.org/link/?jcp
Koopmans-compliant functionals and their performance against reference molecular data
Koopmans-compliant functionals emerge naturally from extending the constraint
of piecewise linearity of the total energy as a function of the number of
electrons to each fractional orbital occupation. When applied to approximate
density-functional theory, these corrections give rise to
orbital-density-dependent functionals and potentials. We show that the simplest
implementations of Koopmans' compliance provide accurate estimates for the
quasiparticle excitations and leave the total energy functional almost or
exactly intact, i.e., they describe correctly electron removals or additions,
but do not necessarily alter the electronic charge density distribution within
the system. Additional functionals can then be constructed that modify the
potential energy surface, including e.g. Perdew-Zunger corrections. These
functionals become exactly one-electron self-interaction free and, as all
Koopmans-compliant functionals, are approximately many-electron
self-interaction free. We discuss in detail these different formulations, and
provide extensive benchmarks for the 55 molecules in the reference G2-1 set,
using Koopmans-compliant functionals constructed from local-density or
generalized-gradient approximations. In all cases we find excellent performance
in the electronic properties, comparable or improved with respect to that of
many-body perturbation theories, such as GW and self-consistent GW, at
a fraction of the cost and in a variational framework that also delivers energy
derivatives. Structural properties and atomization energies preserve or
slightly improve the accuracy of the underlying density-functional
approximations (Note: Supplemental Material is included in the source)
- …