261 research outputs found
Microscopic origins of the ferromagnetic exchange coupling in oxoverdazyl-based Cu(II) complex
The exchange channels governing the experimentally reported coupling constant Jexpt=6 cm−1
value in the verdazyl-ligand based Cu II complex Cu hfac 2 imvdz are inspected using wave
function-based difference dedicated configuration interaction calculations. The interaction between
the two spin 1/2 holders is summed up in a unique coupling constant J. Nevertheless, by gradually
increasing the level of calculation, different mechanisms of interaction are turned on step by step.
In the present system, the calculated exchange interaction then appears alternatively ferromagnetic/
antiferromagnetic/ferromagnetic. Our analysis demonstrates the tremendously importance of some
specific exchange mechanisms. It is actually shown that both parts of the imvdz ligand
simultaneously influence the ferromagnetic behavior which ultimately reaches Jcalc=6.3 cm−1, in
very good agreement with the experimental value. In accordance with the alternation of J, it is
shown that the nature of the magnetic behavior results from competing channels. First, an
antiferromagnetic contribution can be essentially attributed to single excitations involving the
network localized on the verdazyl part. In contrast, the ligand-to-metal charge transfer LMCT
involving the imidazole moiety affords a ferromagnetic contribution. The distinct nature / of the
mechanisms is responsible for the net ferromagnetic behavior. The intuitively innocent part of the
verdazyl-based ligands is deeply reconsidered and opens new routes into the rational design of
magnetic object
Proposal of an extended t-J Hamiltonian for high-Tc cuprates from ab initio calculations on embedded clusters
A series of accurate ab initio calculations on Cu_pO-q finite clusters,
properly embedded on the Madelung potential of the infinite lattice, have been
performed in order to determine the local effective interactions in the CuO_2
planes of La_{2-x}Sr_xCuO_4 compounds. The values of the first-neighbor
interactions, magnetic coupling (J_{NN}=125 meV) and hopping integral
(t_{NN}=-555 meV), have been confirmed. Important additional effects are
evidenced, concerning essentially the second-neighbor hopping integral
t_{NNN}=+110meV, the displacement of a singlet toward an adjacent colinear
hole, h_{SD}^{abc}=-80 meV, a non-negligible hole-hole repulsion
V_{NN}-V_{NNN}=0.8 eV and a strong anisotropic effect of the presence of an
adjacent hole on the values of the first-neighbor interactions. The dependence
of J_{NN} and t_{NN} on the position of neighbor hole(s) has been rationalized
from the two-band model and checked from a series of additional ab initio
calculations. An extended t-J model Hamiltonian has been proposed on the basis
of these results. It is argued that the here-proposed three-body effects may
play a role in the charge/spin separation observed in these compounds, that is,
in the formation and dynamic of stripes.Comment: 24 pages, 4 figures, submitted to Phys. Rev.
Ab initio evaluation of the charge-ordering in
We report {\it ab initio} calculations of the charge ordering in
using large configurations interaction methods on
embedded fragments. Our major result is that the electrons of the
bridging oxygen of the rungs present a very strong magnetic character and
should thus be explicitly considered in any relevant effective model. The most
striking consequence of this result is that the spin and charge ordering differ
substantially, as differ the experimental results depending on whether they are
sensitive to the spin or charge density.Comment: 4 page
Local character of magnetic coupling in ionic solids
Magnetic interactions in ionic solids are studied using parameter-free methods designed to provide accurate energy differences associated with quantum states defining the Heisenberg constant J. For a series of ionic solids including KNiF3, K2NiF4, KCuF3, K2CuF4, and high- Tc parent compound La2CuO4, the J experimental value is quantitatively reproduced. This result has fundamental implications because J values have been calculated from a finite cluster model whereas experiments refer to infinite solids. The present study permits us to firmly establish that in these wide-gap insulators, J is determined from strongly local electronic interactions involving two magnetic centers only thus providing an ab initio support to commonly used model Hamiltonians
Spin Excitations in La2CuO4: Consistent Description by Inclusion of Ring-Exchange
We consider the square lattice Heisenberg antiferromagnet with plaquette ring
exchange and a finite interlayer coupling leading to a consistent description
of the spin-wave excitation spectrum in La2CuO4. The values of the in-plane
exchange parameters, including ring-exchange J_{\Box}, are obtained
consistently by an accurate fit to the experimentally observed in-plane
spin-wave dispersion, while the out-of-plane exchange interaction is found from
the temperature dependence of the sublattice magnetization at low temperatures.
The fitted exchange interactions J=151.9 meV and J_{\Box}=0.24 J give values
for the spin stiffness and the Neel temperature in excellent agreement with the
experimental data.Comment: 4 pages, 1 figure, RevTe
Small Polarons in Transition Metal Oxides
The formation of polarons is a pervasive phenomenon in transition metal oxide
compounds, with a strong impact on the physical properties and functionalities
of the hosting materials. In its original formulation the polaron problem
considers a single charge carrier in a polar crystal interacting with its
surrounding lattice. Depending on the spatial extension of the polaron
quasiparticle, originating from the coupling between the excess charge and the
phonon field, one speaks of small or large polarons. This chapter discusses the
modeling of small polarons in real materials, with a particular focus on the
archetypal polaron material TiO2. After an introductory part, surveying the
fundamental theoretical and experimental aspects of the physics of polarons,
the chapter examines how to model small polarons using first principles schemes
in order to predict, understand and interpret a variety of polaron properties
in bulk phases and surfaces. Following the spirit of this handbook, different
types of computational procedures and prescriptions are presented with specific
instructions on the setup required to model polaron effects.Comment: 36 pages, 12 figure
Hypothalamic miR-30 regulates puberty onset via repression of the puberty-suppressing factor, Mkrn3.
Mkrn3, the maternally imprinted gene encoding the makorin RING-finger protein-3, has recently emerged as putative pubertal repressor, as evidenced by central precocity caused by MKRN3 mutations in humans; yet, the molecular underpinnings of this key regulatory action remain largely unexplored. We report herein that the microRNA, miR-30, with three binding sites in a highly conserved region of its 3' UTR, operates as repressor of Mkrn3 to control pubertal onset. Hypothalamic miR-30b expression increased, while Mkrn3 mRNA and protein content decreased, during rat postnatal maturation. Neonatal estrogen exposure, causing pubertal alterations, enhanced hypothalamic Mkrn3 and suppressed miR-30b expression in female rats. Functional in vitro analyses demonstrated a strong repressive action of miR-30b on Mkrn3 3' UTR. Moreover, central infusion during the juvenile period of target site blockers, tailored to prevent miR-30 binding to Mkrn3 3' UTR, reversed the prepubertal down-regulation of hypothalamic Mkrn3 protein and delayed female puberty. Collectively, our data unveil a novel hypothalamic miRNA pathway, involving miR-30, with a prominent role in the control of puberty via Mkrn3 repression. These findings expand our current understanding of the molecular basis of puberty and its disease states
Ab initio evaluation of local effective interactions in
We will present the numerical evaluation of the hopping and magnetic exchange
integrals for a nearest-neighbor model of the quarter-filled
compound. The effective integrals are obtained from
valence-spectroscopy {\em ab initio} calculations of embedded crystal fragments
(two pyramids in the different geometries corresponding to the desired
parameters). We are using a large configurations interaction (CI) method, where
the CI space is specifically optimized to obtain accurate energy differences.
We show that the system can be seen as a
two-dimensional asymmetric triangular Heisenberg lattice where the effective
sites represent delocalized rung entities supporting the magnetic
electrons.Comment: 24 pages, 5 figure
COVID-19 in hospitalized HIV-positive and HIV-negative patients: A matched study
Objectives: We compared the characteristics and clinical outcomes of hospitalized individuals with COVID-19 with [people with HIV (PWH)] and without (non-PWH) HIV co-infection in Spain during the first wave of the pandemic. Methods: This was a retrospective matched cohort study. People with HIV were identified by reviewing clinical records and laboratory registries of 10 922 patients in active-follow-up within the Spanish HIV Research Network (CoRIS) up to 30 June 2020. Each hospitalized PWH was matched with five non-PWH of the same age and sex randomly selected from COVID-19@Spain, a multicentre cohort of 4035 patients hospitalized with confirmed COVID-19. The main outcome was all-cause in-hospital mortality. Results: Forty-five PWH with PCR-confirmed COVID-19 were identified in CoRIS, 21 of whom were hospitalized. A total of 105 age/sex-matched controls were selected from the COVID-19@Spain cohort. The median age in both groups was 53 (Q1-Q3, 46-56) years, and 90.5% were men. In PWH, 19.1% were injecting drug users, 95.2% were on antiretroviral therapy, 94.4% had HIV-RNA < 50 copies/mL, and the median (Q1-Q3) CD4 count was 595 (349-798) cells/μL. No statistically significant differences were found between PWH and non-PWH in number of comorbidities, presenting signs and symptoms, laboratory parameters, radiology findings and severity scores on admission. Corticosteroids were administered to 33.3% and 27.4% of PWH and non-PWH, respectively (P = 0.580). Deaths during admission were documented in two (9.5%) PWH and 12 (11.4%) non-PWH (P = 0.800). Conclusions: Our findings suggest that well-controlled HIV infection does not modify the clinical presentation or worsen clinical outcomes of COVID-19 hospitalization.This work was supported by the Instituto de Salud Carlos III (ISCII) (grant no. COV20/00108) and the Spanish AIDS Research Network (RD16/0025), which is included in the Spanish I+D+I Plan and is co- funded by ISCIII- Subdirección General de Evaluación and European Funding for Regional Development (FEDER)S
- …