2,124 research outputs found
Vanadium dioxide : A Peierls-Mott insulator stable against disorder
Vanadium dioxide undergoes a first order metal-insulator transition at 340 K.
In this work, we develop and carry out state of the art linear scaling DFT
calculations refined with non-local dynamical mean-field theory. We identify a
complex mechanism, a Peierls-assisted orbital selection Mott instability, which
is responsible for the insulating M phase, and furthermore survives a
moderate degree of disorder.Comment: 5 pages, 4 figures. Supplementary material 8 pages, 4 figures. This
version (v2) matches that accepted for Physical Review Letters on 16th May
201
Electrostatic considerations affecting the calculated HOMO-LUMO gap in protein molecules.
A detailed study of energy differences between the highest occupied and
lowest unoccupied molecular orbitals (HOMO-LUMO gaps) in protein systems and
water clusters is presented. Recent work questioning the applicability of
Kohn-Sham density-functional theory to proteins and large water clusters (E.
Rudberg, J. Phys.: Condens. Mat. 2012, 24, 072202) has demonstrated vanishing
HOMO-LUMO gaps for these systems, which is generally attributed to the
treatment of exchange in the functional used. The present work shows that the
vanishing gap is, in fact, an electrostatic artefact of the method used to
prepare the system. Practical solutions for ensuring the gap is maintained when
the system size is increased are demonstrated. This work has important
implications for the use of large-scale density-functional theory in
biomolecular systems, particularly in the simulation of photoemission, optical
absorption and electronic transport, all of which depend critically on
differences between energies of molecular orbitals.Comment: 13 pages, 4 figure
Recommended from our members
Permeation of COâ and Nâ through glassy poly(dimethyl phenylene) oxide under steady- and presteady-state conditions
Glassy polymers are often used for gas separations because of their high selectivity. Although the dualâmode permeation model correctly fits their sorption and permeation isotherms, its physical interpretation is disputed, and it does not describe permeation far from steady state, a condition expected when separations involve intermittent renewable energy sources. To develop a more comprehensive permeation model, we combine experiment, molecular dynamics, and multiscale reactionâdiffusion modeling to characterize the timeâdependent permeation of Nâ and COâ through a glassy poly(dimethyl phenylene oxide) membrane, a model system. Simulations of experimental timeâdependent permeation data for both gases in the presteadyâstate and steadyâstate regimes show that both singleâ and dualâmode reactionâdiffusion models reproduce the experimental observations, and that sorbed gas concentrations lag the external pressure rise. The results point to environmentâsensitive diffusion coefficients as a vital characteristic of transport in glassy polymers
Adaptation to the Edge of Chaos in the Self-Adjusting Logistic Map
Self-adjusting, or adaptive systems have gathered much recent interest. We
present a model for self-adjusting systems which treats the control parameters
of the system as slowly varying, rather than constant. The dynamics of these
parameters is governed by a low-pass filtered feedback from the dynamical
variables of the system. We apply this model to the logistic map and examine
the behavior of the control parameter. We find that the parameter leaves the
chaotic regime. We observe a high probability of finding the parameter at the
boundary between periodicity and chaos. We therefore find that this system
exhibits adaptation to the edge of chaos.Comment: 3 figure
ONETEP + TOSCAM: uniting dynamical mean field theory and linear-scaling density functional theory
We introduce the unification of dynamical mean field theory (DMFT) and
linear-scaling density functional theory (DFT), as recently implemented in
ONETEP, a linear-scaling DFT package, and TOSCAM, a DMFT toolbox. This code can
account for strongly correlated electronic behavior while simultaneously
including the effects of the environment, making it ideally suited for studying
complex and heterogeneous systems containing transition metals and lanthanides,
such as metalloproteins. We systematically introduce the necessary formalism,
which must account for the non-orthogonal basis set used by ONETEP. In order to
demonstrate the capabilities of this code, we apply it to carbon
monoxide-ligated iron porphyrin and explore the distinctly quantum-mechanical
character of the iron electrons during the process of photodissociation.Comment: Contains 46 pages and 12 figures, including 5 pages of supplementary
materia
Electrically driven photon emission from individual atomic defects in monolayer WS2.
Quantum dot-like single-photon sources in transition metal dichalcogenides (TMDs) exhibit appealing quantum optical properties but lack a well-defined atomic structure and are subject to large spectral variability. Here, we demonstrate electrically stimulated photon emission from individual atomic defects in monolayer WS2 and directly correlate the emission with the local atomic and electronic structure. Radiative transitions are locally excited by sequential inelastic electron tunneling from a metallic tip into selected discrete defect states in the WS2 bandgap. Coupling to the optical far field is mediated by tip plasmons, which transduce the excess energy into a single photon. The applied tip-sample voltage determines the transition energy. Atomically resolved emission maps of individual point defects closely resemble electronic defect orbitals, the final states of the optical transitions. Inelastic charge carrier injection into localized defect states of two-dimensional materials provides a powerful platform for electrically driven, broadly tunable, atomic-scale single-photon sources
Ultra-rapid carbonylation using palladium(I) dimer precatalysts applied to 11CO-radiolabelling for PET
Gene therapy for progressive familial intrahepatic cholestasis type 3 in a clinically relevant mouse model
Progressive familial intrahepatic cholestasis type 3 (PFIC3) is a rare monogenic disease caused by mutations in the ABCB4 gene, resulting in a reduction in biliary phosphatidylcholine. Reduced biliary phosphatidylcholine cannot counteract the detergent effects of bile salts, leading to cholestasis, cholangitis, cirrhosis and ultimately liver failure. Here, we report results from treating two- or five-week-old Abcb4-/- mice with an AAV vector expressing human ABCB4, resulting in significant decreases of PFIC3 disease biomarkers. All male mice achieved a sustained therapeutic effect up through 12 weeks, but the effect was achieved in only 50% of females. However, two-week-old females receiving a second inoculation three weeks later maintained the therapeutic effect. Upon sacrifice, markers of PFIC3 disease such as, hepatosplenomegaly, biliary phosphatidylcholine and liver histology were significantly improved. Thus, AAV-mediated gene therapy successfully prevented PFIC3 symptoms in a clinically relevant mouse model, representing a step forward in improving potential therapy options for PFIC3 patients
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