5,910 research outputs found
Charge-transfer in time-dependent density-functional theory via spin-symmetry-breaking
Long-range charge-transfer excitations pose a major challenge for
time-dependent density functional approximations. We show that
spin-symmetry-breaking offers a simple solution for molecules composed of
open-shell fragments, yielding accurate excitations at large separations when
the acceptor effectively contains one active electron. Unrestricted
exact-exchange and self-interaction-corrected functionals are performed on
one-dimensional models and the real LiH molecule within the pseudopotential
approximation to demonstrate our results.Comment: 5 pages, 4 figure
Universal Dynamical Steps in the Exact Time-Dependent Exchange-Correlation Potential
We show that the exact exchange-correlation potential of time-dependent
density-functional theory displays dynamical step structures that have a
spatially non-local and time non-local dependence on the density. Using
one-dimensional two-electron model systems, we illustrate these steps for a
range of non-equilibrium dynamical situations relevant for modeling of
photo-chemical/physical processes: field-free evolution of a non-stationary
state, resonant local excitation, resonant complete charge-transfer, and
evolution under an arbitrary field. Lack of these steps in usual approximations
yield inaccurate dynamics, for example predicting faster dynamics and
incomplete charge transfer
Approximations based on density-matrix embedding theory for density-functional theories
Recently a novel approach to find approximate exchange–correlation functionals in density-functional theory was presented (Mordovina et al 2019 J. Chem. Theory Comput. 15 5209), which relies on approximations to the interacting wave function using density-matrix embedding theory (DMET). This approximate interacting wave function is constructed by using a projection determined by an iterative procedure that makes parts of the reduced density matrix of an auxiliary system the same as the approximate interacting density matrix. If only the diagonal of both systems are connected this leads to an approximation of the interacting-to-non-interacting mapping of the Kohn–Sham approach to density-functional theory. Yet other choices are possible and allow to connect DMET with other density-functional theories such as kinetic-energy density functional theory or reduced density-matrix functional theory. In this work we give a detailed review of the basics of the DMET procedure from a density-functional perspective and show how both approaches can be used to supplement each other. We do not present a specific realization of combining density-functional methods with DMET but rather provide common grounds to facilitate future developments that encompass both approaches. We do so explicitly for the case of a one-dimensional lattice system, as this is the simplest setting where we can apply DMET and the one that was originally presented. Among others we highlight how the mappings of density-functional theories can be used to identify uniquely defined auxiliary systems and projections in DMET and how to construct approximations for different density-functional theories using DMET inspired projections. Such alternative approximation strategies become especially important for density-functional theories that are based on non-linearly coupled observables such as kinetic-energy density-functional theory, where the Kohn–Sham fields are no longer obtainable by functional differentiation of an energy expression, or for reduced density-matrix functional theories, where a straightforward Kohn–Sham construction is not feasible
Self-Consistent Density-Functional Embedding: A Novel Approach for Density-Functional Approximations
In the present work, we introduce a self-consistent density-functional embedding technique, which leaves the realm of standard energy-functional approaches in density functional theory and targets directly the density-to-potential mapping that lies at its heart. Inspired by the density matrix embedding theory, we project the full system onto a set of small interacting fragments that can be solved accurately. Based on the rigorous relation of density and potential in density functional theory, we then invert the fragment densities to local potentials. Combining these results in a continuous manner provides an update for the Kohn–Sham potential of the full system, which is then used to update the projection. We benchmark our approach for molecular bond stretching in one and two dimensions and show that, in these cases, the scheme converges to accurate approximations for densities and Kohn–Sham potentials. We demonstrate that the known steps and peaks of the exact exchange-correlation potential are reproduced by our method with remarkable accuracy
Carbon Nanotubes Band Assignation, Topology, Bloch States and Selection Rules
Various properties of the energy band structures (electronic, phonon, etc.),
including systematic band degeneracy, sticking and extremes, following from the
full line group symmetry of the single-wall carbon nanotubes are established.
The complete set of quantum numbers consists of quasi momenta (angular and
linear or helical) and parities with respect to the z-reversal symmetries and,
for achiral tubes, the vertical plane. The assignation of the electronic bands
is performed, and the generalized Bloch symmetry adapted eigen functions are
derived. The most important physical tensors are characterized by the same set
of quantum numbers. All this enables application of the presented exhaustive
selection rules. The results are discussed by some examples, e.g. allowed
interband transitions, conductivity, Raman tensor, etc.Comment: 11 pages, 2 figures, 2 tables; pdf available from:
http://www.ff.bg.ac.yu/qmf/qsg_e.ht
Electromechanics of charge shuttling in dissipative nanostructures
We investigate the current-voltage (IV) characteristics of a model
single-electron transistor where mechanical motion, subject to strong
dissipation, of a small metallic grain is possible. The system is studied both
by using Monte Carlo simulations and by using an analytical approach. We show
that electromechanical coupling results in a highly nonlinear IV-curve. For
voltages above the Coulomb blockade threshold, two distinct regimes of charge
transfer occur: At low voltages the system behave as a static asymmetric double
junction and tunneling is the dominating charge transfer mechanism. At higher
voltages an abrupt transition to a new shuttle regime appears, where the grain
performs an oscillatory motion back and forth between the leads. In this regime
the current is mainly mediated by charges that are carried on the grain as it
moves from one lead to the other.Comment: 8 pages, 10 figures, final version to be published in PR
Diazoxide-responsive hyperinsulinemic hypoglycemia caused by HNF4A gene mutations
Objective: The phenotype associated with heterozygous HNF4A gene mutations has recently been extended to include diazoxide responsive neonatal hypoglycemia in addition to maturity-onset diabetes of the young (MODY). To date, mutation screening has been limited to patients with a family history consistent with MODY. In this study, we investigated the prevalence of HNF4A mutations in a large cohort of patients with diazoxide responsive hyperinsulinemic hypoglycemia (HH).
Subjects and methods: We sequenced the ABCC8, KCNJ11, GCK, GLUD1, and/or HNF4A genes in 220 patients with HH responsive to diazoxide. The order of genetic testing was dependent upon the clinical phenotype.
Results: A genetic diagnosis was possible for 59/220 (27%) patients. KATP channel mutations were most common (15%) followed by GLUD1 mutations causing hyperinsulinism with hyperammonemia (5.9%), and HNF4A mutations (5%). Seven of the 11 probands with a heterozygous HNF4A mutation did not have a parent affected with diabetes, and four de novo mutations were confirmed. These patients were diagnosed with HI within the first week of life (median age 1 day), and they had increased birth weight (median +2.4 SDS). The duration of diazoxide treatment ranged from 3 months to ongoing at 8 years.
Conclusions: In this large series, HNF4A mutations are the third most common cause of diazoxide responsive HH. We recommend that HNF4A sequencing is considered in all patients with diazoxide responsive HH diagnosed in the first week of life irrespective of a family history of diabetes, once KATP channel mutations have been excluded
Anomalous insulator metal transition in boron nitride-graphene hybrid atomic layers
The study of two-dimensional (2D) electronic systems is of great fundamental
significance in physics. Atomic layers containing hybridized domains of
graphene and hexagonal boron nitride (h-BNC) constitute a new kind of
disordered 2D electronic system. Magneto-electric transport measurements
performed at low temperature in vapor phase synthesized h-BNC atomic layers
show a clear and anomalous transition from an insulating to a metallic behavior
upon cooling. The observed insulator to metal transition can be modulated by
electron and hole doping and by the application of an external magnetic field.
These results supported by ab-initio calculations suggest that this transition
in h-BNC has distinctly different characteristics when compared to other 2D
electron systems and is the result of the coexistence between two distinct
mechanisms, namely, percolation through metallic graphene networks and hopping
conduction between edge states on randomly distributed insulating h-BN domains.Comment: 9 pages, 15 figure
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