Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userReal-space charge distribution of the cobalt ion and its relation with charge and spin states
114
0
0.0
(
0
)
Authors
Bongjae Kim
Ask ChatGPT about the research
No Arabic abstract
The charge state of an ion provides a simplified electronic picture of the bonding in compounds, and heuristically explains the basic electronic structure of a system. Despite its usefulness, the physical and chemical definition of a charge state is not a trivial one, and the essential idea of electron transfer is found to be not a realistic explanation. Here, we study the real-space charge distribution of a cobalt ion in its various charge and spin states, and examine the relation between the formal charge/spin states and the static charge distribution. Taking the prototypical cobalt oxides, La/SrCoO$_3$, and bulk Co metal, we confirm that no prominent static charge transfer exists for different charge states. However, we show that small variations exist in the integrated charges for different charge states, and these are compared to the various spin state cases.
rate research
Read More
Using 23Na NMR measurements on sodium cobaltates at intermediate dopings (0.44<=x<=0.62), we establish the qualitative change of behavior of the local magnetic susceptibility at x*=0.63-0.65, from a low x Pauli-like regime to the high x Curie-Weiss regime. For 0.5<=x<=0.62, the presence of a maximum T* in the temperature dependence of the susceptibility shows the existence of an x-dependent energy scale. T_1 relaxation measurements establish the predominantly antiferromagnetic character of spin correlations for x<x*. This contradicts the commonly assumed uncorrelated Pauli behavior in this x range and is at odds with the observed ferromagnetic correlations for x>x*. It is suggested that at a given x the ferromagnetic correlations might dominate the antiferromagnetic ones above T*. From 59Co NMR data, it is shown that moving towards higher x away from x=0.5 results in the progressive appearance of nonmagnetic Co3+ sites, breaking the homogeneity of Co states encountered for x<=0.5. The main features of the NMR-detected 59Co quadrupolar effects, together with indications from the powder x-ray diffraction data, lead us to sketch a possible structural origin for the Co3+ sites. In light of this ensemble of new experimental observations, a new phase diagram is proposed, taking into account the systematic presence of correlations and their x-dependence.
The alignment of the Fermi level of a metal electrode within the gap of the hi ghest occupied (HOMO) and lowest unoccupied orbital (LUMO) of a molecule is a key quantity in molecular electronics, which can vary the electron transparency of a single molecule junction by orders of magnitude. We present a quantitative analysis of the relation between this level alignment (which can be estimated from charging free molecules) and charge transfer for bipyridine and biphenyl dithiolate (BPDT) molecules attached to gold leads based on density functional theory calculations. For both systems the charge distribution is defined by a balance between Pauli repulsion with subsequent electrostatic screening and the filling of the LUMO, where bipyridine loses electrons to the leads and BPDT gains electrons. As a direct consequence the Fermi level of the metal is found close to the LUMO for bipyridine and close to the HOMO for BPDT.
Via spin-polarized scanning tunneling microscopy, we revealed a long-range ordered spin density wave (SDW) for the first time on a Cr (001) surface, corresponding to the well-known incommensurate SDW of bulk Cr. It displays a (~ 6.0 nm) long-period spin modulation in each (001) plane and an anti-phase behavior between adjacent planes, which are confirmed by changing the magnetization of the tip. Meanwhile, we simultaneously observed the coexisting charge density wave (CDW) with half the period of the SDW. Taking advantage of real-space measurement, we found the charge and spin modulations are in-phase, and their domain structures are highly correlated. Surprisingly, the phase of CDW in dI/dV map displays a {pi} shift around a density-of-states dip at about -22 meV, indicating an anomalous CDW gap opened below EF. These observations support that the CDW is a secondary order driven by SDW. Therefore, our work is not only the first real space characterization of incommensurate SDW, but also provide new insights on how SDW and CDW coexist.
Recently the charge density wave (CDW) in vanadium dichalcogenides have attracted increasing research interests, but a real-space investigation on the symmetry breaking of the CDW state in VTe2 monolayer is still lacking. We have investigated the CDW of VTe2 monolayer by low energy electron diffraction (LEED) and scanning tunneling microscope (STM). While the LEED experiments revealed a (4X4) CDW transition at 192+-2 K, our low-temperature STM experiments resolved the (4X4) lattice distortions and charge-density modulation in real space, and further unveiled a 1D modulation that breaks the three-fold rotational and mirror symmetries in the CDW state. In accordance with the CDW state at low temperature, a CDW gap of 12 meV was detected by scanning tunneling spectroscopy (STS) at 4.9 K. Our work provides real-space evidence on the symmetry breaking of the (4X4) CDW state in VTe2 monolayer, and implies there is a certain mechanism, beyond the conventional Fermi surface nesting or the q-dependent electron-phonon coupling, is responsible for the formation of CDW state in VTe2 monolayer.
Standard X-ray crystallography methods use free-atom models to calculate mean unit cell charge densities. Real molecules, however, have shared charge that is not captured accurately using free-atom models. To address this limitation, a charge density model of crystalline urea was calculated using high-level quantum theory and was refined against publicly available ultra high-resolution experimental Bragg data, including the effects of atomic displacement parameters. The resulting quantum crystallographic model was compared to models obtained using spherical atom or multipole methods. Despite using only the same number of free parameters as the spherical atom model, the agreement of the quantum model with the data is comparable to the multipole model. The static, theoretical crystalline charge density of the quantum model is distinct from the multipole model, indicating the quantum model provides substantially new information. Hydrogen thermal ellipsoids in the quantum model were very similar to those obtained using neutron crystallography, indicating that quantum crystallography can increase the accuracy of the X-ray crystallographic atomic displacement parameters. The results demonstrate the feasibility and benefits of integrating fully periodic quantum charge density calculations into ultra high-resolution X-ray crystallographic model building and refinement.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
