85 research outputs found
Nickel(II) 3,4;9,10-Perylenediimide bis-Phosphonate Pentahydrate: A MetalâOrganic Ferromagnetic Dye
The new metalâorganic compound nickel(II) 3,4;9,10-
perylenediimide bis-phosphonate pentahydrate, i.e. Ni2[(PDI-BP)-
(H2O)2]·3H2O (1), has been synthesized and its structural and magnetic
properties have been studied. Reaction of 3,4;9,10-perylenediimide bisphosphonate
(PDI-BP, hereafter) ligand and nickel chloride in water resulted
in the precipitation of a red and poorly crystalline solid (1). As the solid shows
a poor crystalline organization of aggregates, the energy dispersive X-ray
diffraction analysis (EDXD) technique has been used to obtain short-range
order structural information of the single nanoaggregates by radial distribution
function analysis. The overall structure of the compound is characterized by
layers containing perylene planes shifted in the direction perpendicular to the
stacking axes in such a way that only the outer rings overlap. The edges of the
perylene planes are connected to the phosphonate groups through an imido
group. The oxygen atoms of the [âPO3]2â group and those of the water
molecules are bonded to the nickel ions resulting in a [NiO6] octahedral coordination sphere. The NiâO bond lengths are 0.21
± 0.08 nm and the NiâOâNi angles of aligned moieties are 95 ± 2°. The oxygen atoms of the water molecules and the nickel
atoms are nearly planar and almost perpendicular to the perylene planes forming chains of edge-sharing octahedra. The magnetic
properties of (1) show the presence of intrachain ferromagnetic NiâNi interactions and a long-range ferromagnetic order below
21 K with a canting angle and with a spin glasslike behavior due to disorder in the inorganic layer. Hysteresis cycles show a
coercive field of ca. 272 mT at 2 K that decreases as the temperature is increased and vanishes at ca. 20 K
Competing Ground States of the New Class of Halogen-Bridged Metal Complexes
Based on a symmetry argument, we study the ground-state properties of
halogen-bridged binuclear metal chain complexes. We systematically derive
commensurate density-wave solutions from a relevant two-band Peierls-Hubbard
model and numerically draw the the ground-state phase diagram as a function of
electron-electron correlations, electron-phonon interactions, and doping
concentration within the Hartree-Fock approximation. The competition between
two types of charge-density-wave states, which has recently been reported
experimentally, is indeed demonstrated.Comment: 4 pages, 5 figures embedded, to appear in J. Phys. Soc. Jp
Pressure-induced phase transitions of halogen-bridged binuclear metal complexes R_4[Pt_2(P_2O_5H_2)_4X]nH_2O
Recent contrasting observations for halogen (X)-bridged binuclear platinum
complexes R_4[Pt_2(P_2O_5H_2)_4X]nH_2O, that is, pressure-induced Peierls and
reverse Peierls instabilities, are explained by finite-temperature Hartree-Fock
calculations. It is demonstrated that increasing pressure transforms the
initial charge-polarization state into a charge-density-wave state at high
temperatures, whereas the charge-density-wave state oppositely declines with
increasing pressure at low temperatures. We further predict that
higher-pressure experiments should reveal successive phase transitions around
room temperature.Comment: 5 pages, 4 figures embedded, to be published in Phys. Rev. B 64,
September 1 (2001) Rapid Commu
Quantum and Thermal Phase Transitions of Halogen-Bridged Binuclear Transition-Metal Complexes
Aiming to settle the controversial observations for halogen-bridged binuclear
transition-metal (MMX) complexes, finite-temperature Hartree-Fock calculations
are performed for a relevant two-band Peierls-Hubbard model. Thermal, as well
as quantum, phase transitions are investigated with particular emphasis on the
competition between electron itinerancy, electron-phonon interaction and
electron-electron correlation. Recently observed distinct thermal behaviors of
two typical MMX compounds Pt_2(CH_3CS_2)_4I and
(NH_4)_4[Pt_2(P_2O_5H_2)_4I]2H_2O are supported and further tuning of their
electronic states is predicted.Comment: 5 pages, 3 figures embedded, to be published in J. Phys. Soc. Jpn.
Vol.70, No.5 (2001
Soliton excitations in halogen-bridged mixed-valence binuclear metal complexes
Motivated by recent stimulative observations in halogen (X)-bridged binuclear
transition-metal (M) complexes, which are referred to as MMX chains, we study
solitons in a one-dimensional three-quarter-filled charge-density-wave system
with both intrasite and intersite electron-lattice couplings. Two distinct
ground states of MMX chains are reproduced and the soliton excitations on them
are compared. In the weak-coupling region, all the solitons are degenerate to
each other and are uniquely scaled by the band gap, whereas in the
strong-coupling region, they behave differently deviating from the scenario in
the continuum limit. The soliton masses are calculated and compared with those
for conventional mononuclear MX chains.Comment: 9 pages, 10 figures embedded, to be published in J. Phys. Soc. Jpn.
71, No. 1 (2002
Experimental Evidence of a Haldane Gap in an S = 2 Quasi-linear Chain Antiferromagnet
The magnetic susceptibility of the quasi-linear chain Heisenberg
antiferromagnet (2,-bipyridine)trichloromanganese(III), MnCl_{3}(bipy), has
been measured from 1.8 to 300 K with the magnetic field, H, parallel and
perpendicular to the chains. The analyzed data yield and K. The magnetization, M, has been studied at 30 mK and 1.4 K in H up to 16
T. No evidence of long-range order is observed. Depending on crystal
orientation, at 30 mK until a critical field is achieved ( and $H_{c\bot} = 1.8\pm 0.2 T), where M increases continuously
as H is increased. These results are interpreted as evidence of a Haldane gap.Comment: 11 pages, 4 figure
Suppression of Jahn-Teller distortion by chromium and magnesium doping in spinel LiMn2O4: A first-principles study using GGA and GGA+U
The effect of doping spinel LiMn2O4 with chromium and magnesium has been
studied using the first-principles spin density functional theory within GGA
(generalized gradient approximation) and GGA+U. We find that GGA and GGA+U give
different ground states for pristine LiMn2O4 and same ground state for doped
systems. For LiMn2O4 the body centered tetragonal phase was found to be the
ground state structure using GGA and face centered orthorhombic using GGA+U,
while for LiM0.5Mn1.5O4 (M= Cr or Mg) it was base centered monoclinic and for
LiMMnO4 (M= Cr or Mg) it was body centered orthorhombic in both GGA and GGA+U.
We find that GGA predicts the pristine LiMn2O4 to be metallic while GGA+U
predicts it to be the insulating which is in accordance with the experimental
observations. For doped spinels, GGA predicts the ground state to be half
metallic while GGA+U predicts it to be insulating or metallic depending on the
doping concentration. GGA+U predicts insulator-metal-insulator transition as a
function of doping in case of Cr and in case of Mg the ground state is found to
go from insulating to a half metallic state as a function of doping. Analysis
of the charge density and the density of states suggest a charge transfer from
the dopants to the neighboring oxygen atoms and manganese atoms. We have
calculated the Jahn-Teller active mode displacement Q3 for doped compounds
using GGA and GGA+U. The bond lengths calculated from GGA+U are found to be in
better agreement with the experimental bond lengths. Based on the bond lengths
of metal and oxygen, we have also estimated the average oxidation states of the
dopants.Comment: 26 pages, 8 figure
Reference Force Field and CDW Amplitude of Mixed-Valence Halogen-Bridged Pt Complexes
The spectroscopic effects of electron-phonon coupling in mixed-valence
chlorine-bridged Pt chains complexes are investigated through a parallel
infrared and Raman study of three compounds with decreasing Pt-Pt distance
along the chain. The e-ph interaction is analyzed in terms of the
Herzberg-Teller coupling scheme. We take into account the quadratic term and
define a precise reference state. The force field relevant to this state is
constructed, whereas the electronic structure is analyzed in terms of a simple
phenomenological model, singling out a trimeric unit along the chain. In this
way we are able to account for all the available optical data of the three
compounds, and to estimate the relevant microscopic parameters, such as the
e-ph coupling constants and the CDW amplitude.Comment: 10 pages, compressed postscript, 6 Tables and 5 Figures also in a
compressed ps.Z file. Revision is in the submission format only (postscript
instead of tex
Self-control interventions for children under age 10 for improving self-control and delinquency and problem behaviors
Self-control improvement programs are intended to serve many purposes, most
notably improving self-control. Yet, interventions such as these often aim to reduce
delinquency and problem behaviors. However, there is currently no summary
statement available regarding whether or not these programs are effective in
improving self-control and reducing delinquency and problem behaviors. The main objective of this review is to assess the available research evidence on the
effect of self-control improvement programs on self-control and delinquency and
problem behaviors. In addition to investigating the overall effect of early selfcontrol
improvement programs, this review will examine, to the extent possible, the
context in which these programs may be most successful. The studies included in this systematic review indicate that self-control
improvement programs are an effective intervention for improving self-control and
reducing delinquency and problem behaviors, and that the effect of these programs
appears to be rather robust across various weighting procedures, and across context,
outcome source, and based on both published and unpublished data
Progress on lead-free metal halide perovskites for photovoltaic applications: a review
ABSTRACT: Metal halide perovskites have revolutionized the field of solution-processable photovoltaics. Within just a few years, the power conversion efficiencies of perovskite-based solar cells have been improved significantly to over 20%, which makes them now already comparably efficient to silicon-based photovoltaics. This breakthrough in solution-based photovoltaics, however, has the drawback that these high efficiencies can only be obtained with lead-based perovskites and this will arguably be a substantial hurdle for various applications of perovskite-based photovoltaics and their acceptance in society, even though the amounts of lead in the solar cells are low. This fact opened up a new research field on lead-free metal halide perovskites, which is currently remarkably vivid. We took this as incentive to review this emerging research field and discuss possible alternative elements to replace lead in metal halide perovskites and the properties of the corresponding perovskite materials based on recent theoretical and experimental studies. Up to now, tin-based perovskites turned out to be most promising in terms of power conversion efficiency; however, also the toxicity of these tin-based perovskites is argued. In the focus of the research community are other elements as well including germanium, copper, antimony, or bismuth, and the corresponding perovskite compounds are already showing promising properties. GRAPHICAL ABSTRACT: [Image: see text
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