172,726 research outputs found
AIRBED: a simplified density functional theory model for physisorption on surfaces
Dispersion interactions are commonly included in density functional theory (DFT) calculations through the addition of an empirical correction. In this study, a modification is made to the damping function in DFT-D2 calculations, to describe repulsion at small internuclear distances. The resulting Atomic Interactions Represented By Empirical Dispersion (AIRBED) approach is used to model the physisorption of molecules on surfaces such as graphene and hexagonal boron nitride, where the constituent atoms of the surface are no longer required to be included explicitly in the density functional theory calculation but are represented by a point charge to capture electrostatic effects. It is shown that this model can reproduce the structures predicted by full DFT-D2 calculations to a high degree of accuracy. The significant reduction in computational cost allows much larger systems to be studied, including molecular arrays on surfaces and sandwich complexes involving organic molecules between two surface layers
Stochastic density functional theory
Linear-scaling implementations of density functional theory (DFT) reach their
intended efficiency regime only when applied to systems having a physical size
larger than the range of their Kohn-Sham density matrix (DM). This causes a
problem since many types of large systems of interest have a rather broad DM
range and are therefore not amenable to analysis using DFT methods. For this
reason, the recently proposed stochastic DFT (sDFT), avoiding exhaustive DM
evaluations, is emerging as an attractive alternative linear-scaling approach.
This review develops a general formulation of sDFT in terms of a
(non)orthogonal basis representation and offers an analysis of the statistical
errors (SEs) involved in the calculation. Using a new Gaussian-type basis-set
implementation of sDFT, applied to water clusters and silicon nanocrystals, it
demonstrates and explains how the standard deviation and the bias depend on the
sampling rate and the system size in various types of calculations. We also
develop basis-set embedded-fragments theory, demonstrating its utility for
reducing the SEs for energy, density of states and nuclear force calculations.
Finally, we discuss the algorithmic complexity of sDFT, showing it has CPU
wall-time linear-scaling. The method parallelizes well over distributed
processors with good scalability and therefore may find use in the upcoming
exascale computing architectures
Implicit Density Functional Theory
A fermion ground state energy functional is set up in terms of particle
density, relative pair density, and kinetic energy tensor density. It satisfies
a minimum principle if constrained by a complete set of compatibility
conditions. A partial set, which thereby results in a lower bound energy under
minimization, is obtained from the solution of model systems, as well as a
small number of exact sum rules. Prototypical application is made to several
one-dimensional spinless non-interacting models. The effectiveness of "atomic"
constraints on model "molecules" is observed, as well as the structure of
systems with only finitely many bound states.Comment: 9 pages, 4 figure
Nonabelian density functional theory
Given a vector space of microscopic quantum observables, density functional
theory is formulated on its dual space. A generalized Hohenberg-Kohn theorem
and the existence of the universal energy functional in the dual space are
proven. In this context ordinary density functional theory corresponds to the
space of one-body multiplication operators. When the operators close under
commutation to form a Lie algebra, the energy functional defines a Hamiltonian
dynamical system on the coadjoint orbits in the algebra's dual space. The
enhanced density functional theory provides a new method for deriving the group
theoretic Hamiltonian on the coadjoint orbits from the exact microscopic
Hamiltonian.Comment: 1 .eps figur
Warming Up Density Functional Theory
Density functional theory (DFT) has become the most popular approach to
electronic structure across disciplines, especially in material and chemical
sciences. Last year, at least 30,000 papers used DFT to make useful predictions
or give insight into an enormous diversity of scientific problems, ranging from
battery development to solar cell efficiency and far beyond. The success of
this field has been driven by usefully accurate approximations based on known
exact conditions and careful testing and validation. In the last decade,
applications of DFT in a new area, warm dense matter, have exploded. DFT is
revolutionizing simulations of warm dense matter including applications in
controlled fusion, planetary interiors, and other areas of high energy density
physics. Over the past decade or so, molecular dynamics calculations driven by
modern density functional theory have played a crucial role in bringing
chemical realism to these applications, often (but not always) with excellent
agreement with experiment. This chapter summarizes recent work from our group
on density functional theory at non-zero temperatures, which we call thermal
DFT. We explain the relevance of this work in the context of warm dense matter,
and the importance of quantum chemistry to this regime. We illustrate many
basic concepts on a simple model system, the asymmetric Hubbard dimer
Spin in Density-Functional Theory
The accurate description of open-shell molecules, in particular of transition
metal complexes and clusters, is still an important challenge for quantum
chemistry. While density-functional theory (DFT) is widely applied in this
area, the sometimes severe limitations of its currently available approximate
realizations often preclude its application as a predictive theory. Here, we
review the foundations of DFT applied to open-shell systems, both within the
nonrelativistic and the relativistic framework. In particular, we provide an
in-depth discussion of the exact theory, with a focus on the role of the spin
density and possibilities for targeting specific spin states. It turns out that
different options exist for setting up Kohn-Sham DFT schemes for open-shell
systems, which imply different definitions of the exchange-correlation energy
functional and lead to different exact conditions on this functional. Finally,
we suggest some possible directions for future developments
Density functional theory of electrowetting
The phenomenon of electrowetting, i.e., the dependence of the macroscopic
contact angle of a fluid on the electrostatic potential of the substrate, is
analyzed in terms of the density functional theory of wetting. It is shown that
electrowetting is not an electrocapillarity effect, i.e., it cannot be
consistently understood in terms of the variation of the substrate-fluid
interfacial tension with the electrostatic substrate potential, but it is
related to the depth of the effective interface potential. The key feature,
which has been overlooked so far and which occurs naturally in the density
functional approach is the structural change of a fluid if it is brought into
contact with another fluid. These structural changes occur in the present
context as the formation of finite films of one fluid phase in between the
substrate and the bulk of the other fluid phase. The non-vanishing Donnan
potentials (Galvani potential differences) across such film-bulk fluid
interfaces, which generically occur due to an unequal partitioning of ions as a
result of differences of solubility contrasts, lead to correction terms in the
electrowetting equation, which become relevant for sufficiently small substrate
potentials. Whereas the present density functional approach confirms the
commonly used electrocapillarity-based electrowetting equation as a good
approximation for the cases of metallic electrodes or electrodes coated with a
hydrophobic dielectric in contact with an electrolyte solution and an ion-free
oil, a significantly reduced tendency for electrowetting is predicted for
electrodes coated with a dielectric which is hydrophilic or which is in contact
with two immiscible electrolyte solutions.Comment: Submitte
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