Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Beyond the Classical Electron-Sharing and Dative Bond Picture: Case of the Spin-Polarized Bond.

ABSTRACT: Chemical bonds are traditionally assigned as electron-sharing or donor-acceptor/dative. External criteria such as the nature of the dissociation process, energy partitioning schemes, or quantum chemical topology are invoked to assess the bonding situation. However, for systems with marked multi-reference character, this binary categorization might not be precise enough to render the bonding properties. A third scenario can be foreseen: spin polarized bonds. To illustrate this, the case of a NaBH₃ ^- cluster is presented. According to the analysis NaBH₃ ^- exhibits a strong diradical character and cannot be classified as either electron-sharing or a dative bond. Elaborated upon are the common problems of popular bonding descriptions. Additionally, a simple model, based on the bond order and local spin indicators, which discriminates between all three bonding situations, is provided.

SUBMITTER: Salvador P

PROVIDER: S-EPMC7839703 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Spin-polarized wide electron slabs in functionally graded polar oxide heterostructures.

Project description:We report on the high mobility wide electron slabs with enhanced correlation effects by tailoring the polarization effects in a functionally graded ZnMgO/ZnO heterostructures. The characteristics of three-dimensional (3D) spreading electrons are evidenced by the capacitance-voltage profiling and the quantization of 3D Fermi surface in magneto-transport measurements. Despite the weak spin-orbit interaction, such electron slabs are spin-polarized with a large zero-field spin splitting energy, which is induced by the carrier-mediated ferromagnetism. Our results suggest that the vast majority of electrons are localized at the surface magnetic moment which does not allow spin manipulations, and only in the region visited by the itinerant carriers that the ferromagnetic exchange interactions via coupling to the surface local moments contribute to the spin transport. The host ferromagnetism is likely due to the formation of Zn cation vacancies on the surface regime induced by the stabilization mechanism and strain-relaxation in ZnMgO polar ionic surface.

| S-EPMC3404416 | biostudies-literature

Double dative bond between divalent carbon(0) and uranium.

Project description:Dative bonds between p- and d-block atoms are common but species containing a double dative bond, which donate two-electron pairs to the same acceptor, are far less common. The synthesis of complexes between UCl4 and carbodiphosphoranes (CDP), which formally possess double dative bonds Cl4U?CDP, is reported in this paper. Single-crystal X-ray diffraction shows that the uranium-carbon distances are in the range of bond lengths for uranium-carbon double bonds. A bonding analysis suggests that the molecules are uranium-carbone complexes featuring divalent carbon(0) ligands rather than uranium-carbene species. The complexes represent rare examples with a double dative bond in f-block chemistry. Our study not only introduces the concept of double dative bonds between carbones and f-block elements but also opens an avenue for the construction of other complexes with double dative bonds, thus providing new opportunities for the applications of f-block compounds.

| S-EPMC6258733 | biostudies-literature

Local electron-electron interaction strength in ferromagnetic nickel determined by spin-polarized positron annihilation.

Project description:We employ a positron annihilation technique, the spin-polarized two-dimensional angular correlation of annihilation radiation (2D-ACAR), to measure the spin-difference spectra of ferromagnetic nickel. The experimental data are compared with the theoretical results obtained within a combination of the local spin density approximation (LSDA) and the many-body dynamical mean-field theory (DMFT). We find that the self-energy defining the electronic correlations in Ni leads to anisotropic contributions to the momentum distribution. By direct comparison of the theoretical and experimental results we determine the strength of the local electronic interaction U in ferromagnetic Ni as 2.0 ± 0.1 eV.

| S-EPMC4754699 | biostudies-other

First spin-resolved electron distributions in crystals from combined polarized neutron and X-ray diffraction experiments.

Project description:Since the 1980s it has been possible to probe crystallized matter, thanks to X-ray or neutron scattering techniques, to obtain an accurate charge density or spin distribution at the atomic scale. Despite the description of the same physical quantity (electron density) and tremendous development of sources, detectors, data treatment software etc., these different techniques evolved separately with one model per experiment. However, a breakthrough was recently made by the development of a common model in order to combine information coming from all these different experiments. Here we report the first experimental determination of spin-resolved electron density obtained by a combined treatment of X-ray, neutron and polarized neutron diffraction data. These experimental spin up and spin down densities compare very well with density functional theory (DFT) calculations and also confirm a theoretical prediction made in 1985 which claims that majority spin electrons should have a more contracted distribution around the nucleus than minority spin electrons. Topological analysis of the resulting experimental spin-resolved electron density is also briefly discussed.

| S-EPMC4086435 | biostudies-literature

Orientation and lipid-peptide interactions of gramicidin A in lipid membranes: polarized attenuated total reflection infrared spectroscopy and spin-label electron spin resonance.

Project description:Gramicidin A was incorporated at a peptide/lipid ratio of 1:10 mol/mol in aligned bilayers of dimyristoyl phosphatidylcholine (DMPC), phosphatidylserine (DMPS), phosphatidylglycerol (DMPG), and phosphatidylethanolamine (DMPE), from trifluoroethanol. Orientations of the peptide and lipid chains were determined by polarized attenuated total reflection infrared spectroscopy. Lipid-peptide interactions with gramicidin A in DMPC bilayers were studied with different spin-labeled lipid species by using electron spin resonance spectroscopy. In DMPC membranes, the orientation of the lipid chains is comparable to that in the absence of peptide, in both gel and fluid phases. In gel-phase DMPC, the effective tilt of the peptide exceeds that of the lipid chains, but in the fluid phase both are similar. For gramicidin A in DMPS, DMPG, and DMPE, the degree of orientation of the peptide and lipid chains is less than in DMPC. In the fluid phase of DMPS, DMPG, and DMPE, gramicidin A is also less well oriented than are the lipid chains. In DMPE especially, gramicidin A is largely disordered. In DMPC membranes, three to four lipids per monomer experience direct motional restriction on interaction with gramicidin A. This is approximately half the number of lipids expected to contact the intramembranous perimeter of the gramicidin A monomer. A selectivity for certain negatively charged lipids is found in the interaction with gramicidin A in DMPC. These results are discussed in terms of the integration of gramicidin A channels in lipid bilayers, and of the interactions of lipids with integral membrane proteins.

| S-EPMC1303987 | biostudies-literature

The pnictogen bond: a quantitative molecular orbital picture.

Project description:We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3PnA- (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A- and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.

| S-EPMC8297534 | biostudies-literature

Thickness Control of the Spin-Polarized Two-Dimensional Electron Gas in LaAlO3/BaTiO3 Superlattices.

Project description:We explored the possibility of increasing the interfacial carrier quantum confinement, mobility and conductivity in the (LaAlO3)n/(BaTiO3)n superlattices by thickness regulation using the first-principles electronic structure calculations. Through constructing two different interfacial types of LaAlO3/BaTiO3 superlattices, we discovered that the LaO/TiO2 interface is preferred from cleavage energy consideration. We then studied the electronic characteristics of two-dimensional electron gas (2DEG) produced at the LaO/TiO2 interface in the LaAlO3/BaTiO3 superlattices via spin-polarized density functional theory calculations. The charge carrier density of 2DEG has a magnitude of 1014?cm-2 (larger than the traditional system LaAlO3/SrTiO3), which is mainly provided by the interfacial Ti 3dxy orbitals when the thicknesses of LaAlO3 and BaTiO3 layers are over 4.5 unit cells. We have also revealed the interfacial electronic characteristics of the LaAlO3/BaTiO3 system, by showing the completely spin-polarized 2DEG mostly confined at the superlattice interface. The interfacial charge carrier mobility and conductivity are found to be converged beyond the critical thickness. Therefore, we can regulate the interfacial confinement for the spin-polarized 2DEG and quantum transport properties in LaAlO3/BaTiO3 superlattice via controlling the thicknesses of the LaAlO3 and BaTiO3 layers.

| S-EPMC5765129 | biostudies-other

Digital electron diffraction--seeing the whole picture.

Project description:The advantages of convergent-beam electron diffraction for symmetry determination at the scale of a few nm are well known. In practice, the approach is often limited due to the restriction on the angular range of the electron beam imposed by the small Bragg angle for high-energy electron diffraction, i.e. a large convergence angle of the incident beam results in overlapping information in the diffraction pattern. Techniques have been generally available since the 1980s which overcome this restriction for individual diffracted beams, by making a compromise between illuminated area and beam convergence. Here a simple technique is described which overcomes all of these problems using computer control, giving electron diffraction data over a large angular range for many diffracted beams from the volume given by a focused electron beam (typically a few nm or less). The increase in the amount of information significantly improves the ease of interpretation and widens the applicability of the technique, particularly for thin materials or those with larger lattice parameters.

| S-EPMC3686228 | biostudies-literature

A Very Short Uranium(IV)-Rhodium(I) Bond with Net Double-Dative Bonding Character.

Project description:Reaction of [U{C(SiMe3 )(PPh2 )}(BIPM)(?-Cl)Li(TMEDA)(?-TMEDA)0.5 ]2 (BIPM=C(PPh2 NSiMe3 )2 ; TMEDA=Me2 NCH2 CH2 NMe2 ) with [Rh(?-Cl)(COD)]2 (COD=cyclooctadiene) affords the heterotrimetallic UIV -RhI2 complex [U(Cl)2 {C(PPh2 NSiMe3 )(PPh[C6 H4 ]NSiMe3 )}{Rh(COD)}{Rh(CH(SiMe3 )(PPh2 )}]. This complex has a very short uranium-rhodium distance, the shortest uranium-rhodium bond on record and the shortest actinide-transition metal bond in terms of formal shortness ratio. Quantum-chemical calculations reveal a remarkable RhI?? UIV net double dative bond interaction, involving RhI 4dz2 - and 4dxy/xz -type donation into vacant UIV 5f orbitals, resulting in a Wiberg/Nalewajski-Mrozek U-Rh bond order of 1.30/1.44, respectively. Despite being, formally, purely dative, the uranium-rhodium bonding interaction is the most substantial actinide-metal multiple bond yet prepared under conventional experimental conditions, as confirmed by structural, magnetic, and computational analyses.

| S-EPMC6055764 | biostudies-other

Spin-polarized oxygen evolution reaction under magnetic field.

Project description:The oxygen evolution reaction (OER) is the bottleneck that limits the energy efficiency of water-splitting. The process involves four electrons' transfer and the generation of triplet state O2 from singlet state species (OH- or H2O). Recently, explicit spin selection was described as a possible way to promote OER in alkaline conditions, but the specific spin-polarized kinetics remains unclear. Here, we report that by using ferromagnetic ordered catalysts as the spin polarizer for spin selection under a constant magnetic field, the OER can be enhanced. However, it does not applicable to non-ferromagnetic catalysts. We found that the spin polarization occurs at the first electron transfer step in OER, where coherent spin exchange happens between the ferromagnetic catalyst and the adsorbed oxygen species with fast kinetics, under the principle of spin angular momentum conservation. In the next three electron transfer steps, as the adsorbed O species adopt fixed spin direction, the OER electrons need to follow the Hund rule and Pauling exclusion principle, thus to carry out spin polarization spontaneously and finally lead to the generation of triplet state O2. Here, we showcase spin-polarized kinetics of oxygen evolution reaction, which gives references in the understanding and design of spin-dependent catalysts.

| S-EPMC8110536 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data