Atomic Moments Research Articles

Na, Mg, and Ca as promoters for N2O adsorption on char surface: A theoretical study

This study aims to evaluate the impact of Na, Mg and Ca on the adsorption of N2O by char based on density-functional theory (DFT) at M06-2X/6-311G(d) level using pristine zigzag (PZ) char models with and without lactone group. The adsorption energy, the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap, electrostatic potential (ESP), electron density difference (EDD), atomic dipole moment corrected hirshfeld (ADCH) charge, and the weak intermolecular interactions were analyzed. Results show that the metal incorporation has little effect on the carbonaceous structure but significantly promotes the adsorption of N2O on char. Further investigations suggest that the metal incorporation induces more valence electrons, and enhances the electron transfer between the metals and carbon surface, thus facilitating char activity to adsorb N2O. Overall, this study provides new insights into the mechanisms of N2O adsorption by heteroatom-incorporation char.

Dipole Moment of a Superatom.

Homodyne detection is used to measure the (collective) atomic dipole moment for an atomic ensemble that is prepared in a superposition of spatially phased Dicke states having at most two excitations (a so-called "superatom"). Homodyne detection allows one to isolate the contributions to the radiated intensity that depend linearly on the average value of the collective atomic dipole moment operator. Depending on whether the atom-reference field interference is constructive or destructive, either super-Poisson or sub-Poisson statistics for the combined field is observed.

Density Functional Theory Study on Screening and Key Metrics for Non-metallic Oxygen Reduction Catalysts.

This study systematically investigates the oxygen reduction reaction (ORR) catalytic activity of graphene doped with various non-metallic impurities. The non-metal elements include boron (B), silicon (Si), nitrogen (N), phosphorus (P), arsenic (As), oxygen (O), sulfur (S), selenium (Se), tellurium (Te), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). We found that adsorbates tend to adsorb on positively charged impurity atoms. We identified several substrates with good catalytic activity, all of which have an ORR overpotential of around 0.6 V. We further verified the thermodynamic stability of these substrates and found them to be very stable. We summarized the optimal adsorption energies for ORR intermediates O2H, O, and OH to be -1.9, -3.4, and -2.4 eV, respectively, and validated their reasonableness. Finally, we used simple linear functions to fit the relationship between the adsorption energies of O2H, O, and OH and the charge and magnetic moment of the adsorption site atoms. This model can roughly predict the ORR catalytic activity of doped graphene, facilitating the faster screening of excellent ORR catalysts.

Non-stoichimometric square sheets in RSe2−x (x ∼ 1/6) (R = Gd and Tb)

The application of optimal electron count has proven effective in predicting the existence of complex structural topologies containing electron-rich polyanionic networks, including linear and zig-zag chains, square planar structures, and simple cubic lattices of main group elements. In this study, we report the successful synthesis of a new family of magnetic compounds, RSe2−x (x ∼ 1/6) (R = Gd and Tb), using KCl flux. The resulting crystal structure of RSe2−x is tetragonal, exhibiting PbFCl-type symmetry with space group P4/nmm. Chemical composition analysis consistently reveals x ∼ 1/6, indicating chalcogen-deficient square sheets. This observation suggests that RSe2−x adheres to the 14-electron rule, as the total valence electrons per RSe2−x (x ∼ 1/6) is 14 e−. In GdSe2−x (x ∼ 1/6), the magnetic susceptibility measurement displays a lambda-shaped peak around 8 K, indicating an antiferromagnetic-type transition. However, the positive Curie–Weiss temperature (θCW) suggests the presence of an additional ferromagnetic interaction, which may result from the large magnetic moment of the Gd atoms. In contrast, TbSe2−x (x ∼ 1/6) exhibits antiferromagnetic ordering. Chemical bonding analysis also indicates that the strong Se–Se antibonding in the square net may be related to Se deficiency. Our work shed light on ellucidating the interplay between chemical rule, defects, and magnetism.

5d transition-metal adsorption tailored valley splitting and magnetic anisotropy of Janus 2H-WSSe monolayer

Valley splitting and magnetic anisotropy of 5d TM (Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg) adsorbed Janus 2H-WSSe monolayers are investigated using first-principles calculations. The results show that 5d TM atoms adsorbed on the W-top site of Janus 2H-WSSe monolayer exhibit the lowest adsorption energy, regardless of the Se or S layer. The electronic states of Hf-SW and Re-SeW adsorbed systems cross the EF and show metallicity, while the other adsorbed systems still exhibit the semiconducting characteristics. According to the k·p model based on the effective Hamiltonian, the Zeeman effect arising from the local magnetic moment of 5d TM atoms lifts tunable valley splitting within 12.7–227 meV owing to different SOC strength. A maximum valley splitting of 227 meV is observed in the W adsorbed system, which is large enough to realize the valley Hall effect. Both perpendicular magnetic anisotropy (PMA) and in-plane magnetic anisotropy (IMA) can be adjusted by adsorbing different 5d TM atoms on the S/Se layer. Remarkably, the matrix elements differences (dx2–y2, dxy) decide the PMA and IMA behaviors, which are due to the competition of different TM-d orbitals based on the second-order perturbation theory. These results suggest that the 5d TM adsorbed Janus 2H-WSSe monolayer can be considered a good candidate for the spintronic and valleytronic devices.

Towards atom counting from first moment STEM images: Methodology and possibilities

Through a simulation-based study we develop a statistical model-based quantification method for atomic resolution first moment scanning transmission electron microscopy (STEM) images. This method uses the uniformly weighted least squares estimator to determine the unknown structure parameters of the images and to isolate contributions from individual atomic columns. In this way, a quantification of the projected potential per atomic column is achieved. Since the integrated projected potential of an atomic column scales linearly with the number of atoms it contains, it can serve as a basis for atom counting. The performance of atom counting from first moment STEM imaging is compared to that from traditional HAADF STEM in the presence of noise. Through this comparison, we demonstrate the advantage of first moment STEM images to attain more precise atom counts. Finally, we compare the integrated potential extracted from first-moment images of a wedge-shaped sample to those values from the bulk crystal. The excellent agreement found between these values proves the robustness of using bulk crystal simulations as a reference library. This enables atom counting for samples with different shapes by comparison with these library values.

Molten Salt-Assisted Synthesis of Ferric Oxide/M-N-C Nanosheet Electrocatalysts for Efficient Oxygen Reduction Reaction.

Efficient, stable, and low-cost oxygen reduction catalysts are the key to the large-scale application of metal-air batteries. Herein, high-dispersive Fe2O3 nanoparticles (NPs) with abundant oxygen vacancies uniformly are anchored on lignin-derived metal-nitrogen-carbon (M-N-C) hierarchical porous nanosheets as efficient oxygen reduction reaction (ORR) catalysts (Fe2O3/M-N-C, M═Cu, Mn, W, Mo) based on a general and economical KCl molten salt-assisted method. The combination of Fe with the highly electronegative O induces charge redistribution through the Fe-O-M structure, thereby reducing the adsorption energy of oxygen-containing substances. The coupling effect of Fe2O3 NPs with M-N-C expedites the catalytic activity toward ORR by promoting proton generation on Fe2O3 and transfer to M-N-C. Experimental and theoretical calculation further revealed the remarkable electronic structure evolution of the metal site during the ORR process, where the emission density and local magnetic moment of the metal atoms change continuously throughout their reaction. The unique layered porous structure and highly active M-N4 sites resulted in the excellent ORR activity of Fe2O3/Cu-N-C with the onset potential of 0.977V, which is superior to Pt/C. This study offers a feasible strategy for the preparation of non-noble metal catalysts and provides a new comprehension of the catalytic mechanism of M-N-C catalysts.

ADCHα-I population analysis and constrained dipole moment density functional theory in force fields for molecular simulations.

A new population analysis, ADCHα-I, based on the interpolation between the Hirshfeld (H) and the iterative Hirshfeld (H-I) methods through a parameter α and on the atomic dipole moment corrected Hirshfeld (ADCH) methodology is proposed, in combination with the constrained dipole moment density functional theory (CD-DFT) previously developed, to determine the charge distributions of force fields. Following this approach, the electronic density of the isolated molecule is determined for the value of the dipole moment that reproduces the experimental dielectric constant, in order to incorporate through this property the effects of the surrounding molecules in the liquid, and to carry on this information to the molecular simulation, the new population analysis is built to obtain the set of charges that reproduces this dipole moment. By selecting α = 1/2, one is led to charges that are larger than the ones obtained through H and ADCH and smaller than those of H-I and that incorporate, at the local level, information about the response of isolated atoms to donate or to accept charge, which is not considered in ADCH. The results obtained for several liquid properties indicate that the combination of CD-DFT with this population analysis leads to a good description of the charge distributions in force fields used in molecular simulations.

Ab Initio Study of the Influence of Spin and Orbital Magnetic Moments on the Stability of Magnetic and Charge Distribution in Co:ZnO Monolayer.

The development of ultrathin magnets with tunable magnetic properties is essential for advancing quantum computing technologies. In this study, density functional theory (DFT) calculations were employed to investigate the atomic and electronic structures of a ZnO monolayer embedded with cobalt atoms. The impact of spin dynamics on charge transfer within the Co:ZnO system was thoroughly examined. Results revealed that the orbital magnetic moment of the cobalt atoms plays a crucial role in stabilizing the magnetic and charge distributions across the system. These findings offer valuable insights for the design and fabrication of quantum devices, thereby highlighting the potential of Co-doped ZnO monolayers in quantum computing applications.

Composition and microstructure engineering of Fe–Si–Co soft magnetic alloys with enhanced performance

The growing demand for high-efficiency and low-loss energy conversion and transportation techniques urges the development of advanced Fe–Si based soft magnet alloys. Simultaneous achievement of low coercivity (Hc) and large saturation magnetization (Ms) however, remains challenging. In this study, soft magnetic alloys with the composition Fe82–xSi18Cox (x = 0 at.%, 4 at.%, 8 at.%, 12 at.%, 16 at.%, and 20 at.%) have been designed followed by microstructural tuning. The Co incorporation results in initially decreased Hc followed by increment due to reduced magnetocrystalline anisotropy and increased saturation magnetostriction from negative to positive values of the alloys. Meanwhile, the Ms raises with subsequent reduction, which origins from competitive mechanisms of increased average moment of Fe atoms and decreased average moment of Co atoms according to first principles calculations. Microstructural evolution during annealing of the Fe70Si18Co12 with synergistically optimized Hc and Ms has been revealed that after elevated-temperature annealing, the DO3 phase is predominately transformed from the B2 phase accompanied by an increase in the degree of ordering. The growth of the DO3 phase deteriorates the Hc due to the aggravating pinning effect on the domain wall movement, which arises from the inhomogeneous magnetization distribution caused by increasing antiphase boundaries.

Calculation on power factor and figure of merit in a single-layer NiBr2

Abstract Implementation of the classical Boltzmann transport theory has been performed to calculate the power factor, as well as the figure of merit in a single-layer NiBr2 after performing density functional theory. Those two properties were formulated from the Seebeck coefficient, electron thermal conductivity, and electrical conductivity. An in-plane ferromagnetic formation of magnetic moments in the Ni atoms was applied in the primitive cell. We found a small power factor, but a high figure of merit at the Fermi level near critical temperature. Since the efficiency of thermoelectric materials is represented by the figure of merit, a single-layer NiBr2 is a strong candidate for thermoelectric materials which can be applied in future devices.

Effects of transition metals (V, Cr, Mn, Fe and Ni) doping on magnetic properties of Co-based amorphous alloys

Amorphous alloys exhibit numerous interesting and abundant magnetic properties due to their disordered structural traits and have been extensively studied by researchers. In this work, the effects of a small amount of transition metals doping on the magnetic properties of Co80-xMxB20 (x = 0, 2, 4, 6, 8, 10; M = V, Cr, Mn, Fe, Ni) amorphous alloys were systematically investigated by utilizing first-principles molecular dynamics. The trend of the magnetic moment change in the simulated calculation conforms well to the experimental results. The doping of V atoms leads to the fastest rate of decrease in the magnetic moment of the surrounding Co atoms, and there is only an antiferromagnetic interaction between the V and Co atoms. When doped with Cr and Mn atoms, there is mutual competition between ferromagnetic and antiferromagnetic coupling in the amorphous alloy, Cr reduces the magnetic moment of the surrounding Co atoms, while the change in the magnetic moment of the Co atoms around Mn is small. The doping of Fe and Ni causes an increase in the magnetic moment of the surrounding Co atoms. The reason may be due to the charge transfer between atoms. The doping of Fe and Ni has a small effect on the average magnetic moment of the Co atoms in the amorphous alloy. The results provide necessary theoretical support for the development of the Co-based amorphous alloys with excellent magnetic characteristics.

Modeling Intermolecular Interactions with Exchange-Hole Dipole Moment Dispersion Corrections to Neural Network Potentials.

Neural network potentials (NNPs) are an innovative approach for calculating the potential energy and forces of a chemical system. In principle, these methods are capable of modeling large systems with an accuracy approaching that of a high-level ab initio calculation, but with a much smaller computational cost. Due to their training to density-functional theory (DFT) data and neglect of long-range interactions, some classes of NNPs require an additional term to include London dispersion physics. In this Perspective, we discuss the requirements for a dispersion model for use with an NNP, focusing on the MLXDM (Machine Learned eXchange-Hole Dipole Moment) model developed by our groups. This model is based on the DFT-based XDM dispersion correction, which calculates interatomic dispersion coefficients in terms of atomic moments and polarizabilities, both of which can be approximated effectively using neural networks.

Enhancing the antioxidant potential of ESIPT-based naringenin flavonoids based on excited state hydrogen bond dynamics: A theoretical study

Exploring antioxidant potential of flavonoid derivatives after ESIPT process provides a theoretical basis for discovering compounds with higher antioxidant capacity. In this work, employing the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods, the antioxidant potential of two citrus-derived naringenin flavonoids after ESIPT process is explored. Based on studies of ESIPT process including IMHB intensity variations, potential energy curves, and transition state, these molecules exist only in enol and keto⁎ forms due to ultra-fast ESIPT. The HOMOs are utilized to explore electron-donating capacity, demonstrating that the molecules in keto⁎ form is stronger than that in enol form. Furthermore, the atomic dipole moment corrected Hirshfeld population (ADCH) and Fukui functions indicate that the sites attacked by the electrophilic free radical of the two molecules in the keto⁎ form are O3 and O5’ respectively, and both are more active than in the enol form. Overall, a comprehensive consideration of the ESIPT process and antioxidant potential of flavonoid derivatives will facilitate the exploration and design of substances with higher antioxidant capacity.

The surface defect of Fe2Ge (001) induces a synergistic spin effect and regulates the surface magnetism

The defect structure leads to the fracture and recombination of chemical bonds, lattice distortion, electron localization, etc., which has a significant improvement on the physical properties of materials, and give them new functions. The unique structure of Fe2Ge forms the surface structure of Ge end face and Fe end face in the direction of (001), but the surface is easy to form defect structure, and affecting its properties. It is found that the spin direction of Ge atom is opposite to the spin direction of Fe atom in perfect Fe2Ge (001) surface structure. When there is VGe defect, the magnetic moments of the perfect Fe2Ge (001) surface and Fe atoms are enhanced. When there are VFe, VFe-Ge and VGe-Fe defects, the magnetic moments of defects Fe2Ge (001) surface and Fe atoms are weakened. The reason is that the spin state electrons of Fe atoms induce Ge atoms to produce spin electrons, which forms a synergistic spin effect. The Hirshfeld Charge distribution and charge spin of Fe and Ge atoms are affected by the local potential field, Ge atoms are excited with spin direction of Fe atoms with VFe and VFe-Ge, and Ge atoms induce magnetic moments with spin direction of Fe atoms with VGe and VGe-Fe. The effects mechanism is that the five orbitals dzz, dxy, dzy, dzx and dxx-yy of Fe atom are greatly affected by the structure of the defect under the action of crystal field, while the s, px, py and pz orbitals are less affected. In VGe and VFe-Ge defects, the spin splitting of the d orbitals is larger to form a larger magnetic moment. In VFe and VGe-Fe defects, the d orbital spin splitting is smaller, and resulting in a smaller magnetic moment. The s, px, py and pz of Ge atoms are greatly affected, the spin splitting of pz is larger than that of px and py orbitals, and indicating that the spin of Ge atoms mainly comes from pz orbitals.

Radical‐Induced Changes in Transition Metal Interfacial Magnetic Properties: A Blatter Derivative on Polycrystalline Cobalt

AbstractIn this work, we study the interface obtained by depositing a monolayer of a Blatter radical derivative on polycrystalline cobalt. By examining the occupied and unoccupied states at the interface, using soft X‐ray techniques, combined with electronic structure calculations, we could simultaneously determine the electronic structure of both the molecular and ferromagnetic sides of the interface, thus obtaining a full understanding of the interfacial magnetic properties. We found that the molecule is strongly hybridized with the surface. Changes in the core level spectra reflect the modification of the molecule and the cobalt electronic structures inducing a decrease in the magnetic moment of the cobalt atoms bonded to the molecules which, in turn, lose their radical character. Our method allowed us to screen, beforehand, organic/ferromagnetic interfaces given their potential applications in spintronics.

Radical-Induced Changes in Transition Metal Interfacial Magnetic Properties: A Blatter Derivative on Polycrystalline Cobalt.

In this work, we study the interface obtained by depositing a monolayer of a Blatter radical derivative on polycrystalline cobalt. By examining the occupied and unoccupied states at the interface, using soft X-ray techniques, combined with electronic structure calculations, we could simultaneously determine the electronic structure of both the molecular and ferromagnetic sides of the interface, thus obtaining a full understanding of the interfacial magnetic properties. We found that the molecule is strongly hybridized with the surface. Changes in the core level spectra reflect the modification of the molecule and the cobalt electronic structures inducing a decrease in the magnetic moment of the cobalt atoms bonded to the molecules which, in turn, lose their radical character. Our method allowed us to screen, beforehand, organic/ferromagnetic interfaces given their potential applications in spintronics.

Identification and Manipulation of Atomic Polarization Moments for Nonlinear Magneto‐Optical Rotation Atomic Magnetometers

AbstractPolarization moments play a crucial role in measuring magnetic fields for nonlinear magneto‐optical rotation (NMOR) atomic magnetometers. However, it is challenging to distinguish between each polarization moment and evaluate its effect on the magnetic resonance response signal in an alkali vapor cell with buffer gas. To address this issue, a method is proposed to identify different polarization moments through the frequency shift of the magnetic resonance response signal. The proportion of each polarization moment is determined, and it is demonstrated that the magnetic resonance response signal is affected by the hexadecapole moment, resulting in a frequency shift and a decrease in signal amplitude. To mitigate this effect, an approach is investigated to manipulate the polarization moments by flipping the phase of the pump light. Ultimately, a 15.19% increase in response amplitude is achieved in the simulated geomagnetic environment within the magnetic shield barrel. The theory and method presented here provide strong support for the study of the polarization moments in an alkali vapor cell with buffer gas, which potentially enhance the performance of NMOR atomic magnetometers.

Energy Barriers for the Spontaneous Magnetization Reversal of the Atomic Co Chains on Pt(664) Surface in the Model with Dzyaloshinskii–Moriya Interaction

The analytical approach has been developed in the framework of the continuous XY-model. This approach allows calculating the spontaneous magnetization reversal time of finite-length atomic chains on the metallic surface. The interaction of the magnetic moments of atoms is described by the classical Hamiltonian, which includes the Heisenberg exchange interaction, the Dzyaloshinskii–Moriya interaction, and the magnetic anisotropy energy. Using the Co/Pt(664) system as an example, it has been shown that the proposed method is in a good agreement with the results of the numerical simulation in the limit of short and long atomic chains. And for atomic chains of intermediate length, it can be used to estimate an upper bound on the spontaneous magnetization reversal time. We obtained the dependences of the spontaneous magnetization reversal time of finite-length Co chains the value of the exchange integral, parameters of the magnetic anisotropy, and also on the value of the projection of the Dzyaloshinskii vector onto the axis perpendicular to the plane containing the magnetic moments of the atoms. It is shown that the proposed method has a wide range of applicability both in terms of temperature and the values of the physical parameters characterizing the magnetic properties of the atomic chains.

Incorporating Noncovalent Interactions in Transfer Learning Gaussian Process Regression Models for Molecular Simulations.

FFLUX is a quantum chemical topology-based multipolar force field that uses Gaussian process regression machine learning models to predict atomic energies and multipole moments on the fly for fast and accurate molecular dynamics simulations. These models have previously been trained on monomers, meaning that many-body effects, for example, intermolecular charge transfer, are missed in simulations. Moreover, dispersion and repulsion have been modeled using Lennard-Jones potentials, necessitating careful parametrization. In this work, we take an important step toward addressing these shortcomings and show that models trained on clusters, in this case, a dimer, can be used in FFLUX simulations by preparing and benchmarking a formamide dimer model. To mitigate the computational costs associated with training higher-dimensional models, we rely on the transfer of hyperparameters from a smaller source model to a larger target model, enabling an order of magnitude faster training than with a direct learning approach. The dimer model allows for simulations that account for two-body effects, including intermolecular polarization and charge penetration, and that do not require nonbonded potentials. We show that addressing these limitations allows for simulations that are closer to quantum mechanics than previously possible with the monomeric models.