Explicit Polarization Research Articles

PHAHST Potential: Modeling Sorption in a Dispersion-Dominated Environment.

PHAHST (potentials with high accuracy, high speed, and transferability) is a recently developed force field that utilizes exponential repulsion, multiple dispersion terms, explicit many-body polarization, and many-body van der Waals interactions. The result is a systematic approach to force field development that is computationally practical. Here, PHAHST is employed in the simulation for rare gas uptake of krypton and xenon in the metal-organic material, HKUST-1. This material has shown promise in use as an adsorptive separating agent and presents a challenge to model due to the presence of heterogeneous interaction sorption surfaces, which include pores with readily accessible, open-metal sites that compete with dispersion-dominated pores. Such environments are difficult to simulate with commonly used empirical force fields, such as the Lennard-Jones (LJ) potential, which perform better when electrostatics are dominant in determining the nature of sorption and alone are incapable of modeling interactions with open-metal sites. The effectiveness of PHAHST is compared to the LJ potential in a series of mixed Kr-Xe gas simulations. It has been demonstrated that PHAHST compares favorably with experimental results, and the LJ potential is inadequate. Overall, we establish that force fields with physically grounded repulsion/dispersion terms are required in order to accurately model sorption, as these interactions are an important component of the energy. Furthermore, it is shown that the simple mixing rules work nearly quantitatively for the true pair potentials, while they are not transferable for effective potentials like LJ.

The effects of social versus economic ideology similarity information on explicit and implicit political person perception

We tested among Democratic and Republican perceivers the relative effects of social vs. economic ideology similarity information about individual members of the opposing party (i.e., information suggesting that a member of the opposing party has similar social or economic ideological views as the perceiver) on explicit and implicit affective polarization in evaluations of these target individuals and on perceived worldview conflict with these individuals. In Studies 1a and 1b, both types of ideology information reduced explicit affective polarization on some measures. Among both Democratic and Republican perceivers, the two types of similarity information were equally effective at reducing overall worldview conflict. Neither type of ideology information shifted implicit affective polarization (Studies 2a and 2b).

Structure and dynamics of Li1.24K0.76CO3 molten carbonate electrolyte from molecular simulations with explicit polarization.

Molten carbonate electrolysis cells represent a key technology for harnessing surplus energy from renewable sources and converting it into gaseous energy carriers. To optimize their efficiency, a comprehensive understanding of each step in the operational process is essential. Here, we focus on the electrolyte of choice in molten carbonate cells: the Li1.24K0.76CO3 melt. Utilizing molecular dynamics with explicit polarization, we demonstrate that the structure of this molten mixture is characterized by a dense network of lithium-carbonate complexes, with K+ ions loosely embedded within this network. This structural insight enables us to rationalize from an atomistic perspective the conductivity trends observed experimentally in molten carbonates. Moreover, our work highlights the importance of including polarization for the simulations of dense liquid carbonates. It also acts as a foundational step towards more advanced theoretical studies for elucidating the role of the electrolyte in these devices.

Strong and tunable anisotropy in monolayer graphene with broken symmetry

Low-symmetry two-dimensional materials have attracted much attention in recent years due to their exotic and incredible properties. Here, we construct Ta2NiS5-based van der Waals heterostructures to introduce in-plane polarization in monolayer graphene through symmetry engineering. Angle-dependent conductance and mobility measurement combined with theoretical calculations all verify that the pristine Ta2NiS5 possesses prominent electrical anisotropy, with anisotropic ratio (a-axis/c-axis) of about 2.1 in conductivity and 3.28 in mobility. Furthermore, we demonstrate that van der Waals interlayer coupling has induced explicit in-plane polarization in monolayer graphene according to angle-dependent Raman spectroscopy and electrical transport measurement on monolayer-graphene/Ta2NiS5 heterostructures. In polarized graphene, the conductivity and mobility ratios are up to 3.21 and 4.84, respectively. The induced polarization in monolayer graphene within heterostructures probably originates from strain, lattice reconstruction, induced symmetry reduction and charge transfer through van der Waals interfaces. These results might provide inspiration to study symmetry-related van der Waals heterostructures and pave their way to novel nano-electronic devices.

Polarizable AMOEBA Model for Simulating Mg2+·Protein·Nucleotide Complexes.

Molecular mechanics (MM) simulations have the potential to provide detailed insights into the mechanisms of enzymes that utilize nucleotides as cofactors. In most cases, the activities of these enzymes also require the binding of divalent cations to catalytic sites. However, modeling divalent cations in MM simulations has been challenging. The inclusion of explicit polarization was considered promising, but despite improvements over nonpolarizable force fields and despite the inclusion of "Nonbonded-fix (NB-fix)" corrections, errors in interaction energies of divalent cations with proteins remain large. Importantly, the application of these models fails to reproduce the experimental structural data on Mg2+·Protein·ATP complexes. Focusing on these complexes, here we provide a systematic assessment of the polarizable AMOEBA model and recommend critical changes that substantially improve its predictive performance. Our key results are as follows. We first show that our recent revision of the AMOEBA protein model (AMOEBABIO18-HFC), which contains high field corrections (HFCs) to induced dipoles, dramatically improves Mg2+-protein interaction energies, reducing the mean absolute error (MAE) from 17 to 10 kcal/mol. This further supports the general applicability of AMOEBABIO18-HFC. The inclusion of many-body NB-fix corrections further reduces MAE to 6 kcal/mol, which amounts to less than 2% error. The errors are estimated with respect to vdW-inclusive density functional theory that we benchmark against CCSD(T) calculations and experiments. We also present a new model of ATP with revised polarization parameters to better capture its high field response, as well as new vdW and dihedral parameters. The ATP model accurately predicts experimental Mg2+-ATP binding free energy in the aqueous phase and provides new insights into how Mg2+ associates with ATP. Finally, we show that molecular dynamics (MD) simulations of Mg2+·Kinase·ATP complexes carried out with these improvements lead to a better agreement in global and local catalytic site structures between MD and X-ray crystallography.

Molecular Modeling of Water-in-Salt Electrolytes: A Comprehensive Analysis of Polarization Effects and Force Field Parameters in Molecular Dynamics Simulations.

Accurate modeling of highly concentrated aqueous solutions, such as water-in-salt (WiS) electrolytes in battery applications, requires proper consideration of polarization contributions to atomic interactions. Within the force field molecular dynamics (MD) simulations, the atomic polarization can be accounted for at various levels. Nonpolarizable force fields implicitly account for polarization effects by incorporating them into their van der Waals interaction parameters. They can additionally mimic electron polarization within a mean-field approximation through ionic charge scaling. Alternatively, explicit polarization description methods, such as the Drude oscillator model, can be selectively applied to either a subset of polarizable atoms or all polarizable atoms to enhance simulation accuracy. The trade-off between simulation accuracy and computational efficiency highlights the importance of determining an optimal level of accounting for atomic polarization. In this study, we analyze different approaches to include polarization effects in MD simulations of WiS electrolytes, with an example of a Na-OTF solution. These approaches range from a nonpolarizable to a fully polarizable force field. After careful examination of computational costs, simulation stability, and feasibility of controlling the electrolyte properties, we identify an efficient combination of force fields: the Drude polarizable force field for salt ions and non-polarizable models for water. This cost-effective combination is sufficiently flexible to reproduce a broad range of electrolyte properties, while ensuring simulation stability over a relatively wide range of force field parameters. Furthermore, we conduct a thorough evaluation of the influence of various force field parameters on both the simulation results and technical requirements, with the aim of establishing a general framework for force field optimization and facilitating parametrization of similar systems.

Journalism and the regime change in Pakistan (2022): exploring the solidarity and political discourses on the social media

For the first time in Pakistan, a sitting prime minister has been ousted through a ‘No-Confidence Motion (NCM)’ initiated by the Pakistan Democratic Movement (PDM) in April 2022. PDM, the coalition of 15 political parties, claimed the success of NCM as the win of democracy. The ousted PM and Chairman Pakistan Tehreek-e-Insaf, Mr. Imran Khan, alleged that the motion was a ‘regime change’ attempt backed by a foreign conspiracy initiated by internal and external elements. Pakistani journalists, who are already labelled as political partisans, took to the social media platform Twitter, and started spreading the ‘political discourse’ about the removal of Khan from the PM office. This research explores the predominant themes within the discourse produced through the Twitter handles of the selected journalists; Arshad Sharif, Hamid Mir and Mazhar Abbas. Secondly, to determine whether and to what extent the journalists have produced the ‘political discourse’ and or the ‘solidarity discourse’. We have employed thematic analysis as a theoretical and methodological tool to achieve the research objectives. The findings show a clear divide between the journalists and an explicit polarization within the discourse produced through their Twitter posts on the issue, and the solidarity discourse is virtually non-existent.

Transport Parameters for Combustion Species Based on cAMOEBA Polarizable Force Field.

In this study, we report a simplified yet accurate general AMOEBA polarizable force field for combustion-interested molecular species, denoted as Combustion-AMOEBA or cAMOEBA. By eliminating the permanent atomic dipoles and quadrupoles, retaining the explicit polarization and defining the general atom types of each molecule species, including alkanes, alkenes, alkynes, alcohols, peroxides, and aldehydes, a simplified and general cAMOEBA force field was constructed and validated using the benchmark results obtained at the QCISD(T)/CBS level of theory. In this way, the tedious parametrization step for permanent atomic multipoles of each new molecule in the original AMOEBA (Poltype/MP2) force field could be avoided, hence providing the capability of accurate high-throughput calculation for a large number of molecules at lower computational cost. The averaged difference between the calculated transport parameters, σ and ε, for approximately 100 different molecules and four bath gases (He, Ne, Ar, and N2) using cAMOEBA and AMOEBA (Poltype/MP2) are of 0.09% and 1.27%, respectively, showing a good consistence of the general cAMOEBA force field with the original AMOEBA (Poltype/MP2) force field where the multipole force field parameters were obtained from quantum mechanical calculation for each small molecule. Our results also indicated that the Lorentz-Berthelot combination rule was more applicable than Waldman-Hagler for obtaining the molecular Lennard-Jones parameters of pure gases from one bath gas, while the Waldman-Hagler combination rule was better for obtaining such parameters from all four bath gases. The pure gas parameters obtained using cAMOEBA can be applied to develop high quality transport property database for combustion modeling.

Improved polarizable force field for modeling Mg2+ binding to proteins and nucleotides.

Magnesium (Mg2+) is an indispensable regulatory cation for numerous cellular enzymes and membrane proteins that participate in a variety of biological processes, including cell signaling, glycolysis, cell differentiation, and genome stability. Molecular mechanics (MM) simulations have the potential to provide detailed insights into the mechanisms of these Mg-dependent proteins. However, MM force fields continue to suffer from large inaccuracies when dealing with divalent cations. The inclusion of explicit polarization in MM models, such as in CHARMM Drude and AMOEBA models, has been promising, but despite substantial improvements over non-polarizable models, errors in interactions of proteins with divalent cations remain in excess of 10 kcal/mol. Such errors are present even with ‘nonbonded-fix (NB-fix)’ corrections. Modeling becomes even more problematic when dealing with enzymes like kinases and phosphatases, where Mg2+ ions interact directly with both proteins and nucleotides. Toward addressing this long-standing challenge, we recently presented a recalibration of the AMOEBA model (Delgado et al. J Chem. Info. Model. 2022). Notably, polarization terms of cation-coordinating groups were improved to respond better to the high electric fields present near cations. This systematically reduced errors in interactions of monovalent cations with proteins. Here we show that this revised model, along with our many body NB-fix (MB-NB-fix) corrections, reduces errors in Mg2+-protein interaction energies to 5 kcal/mol. MB-NB-fix corrections also improve predictions of Mg2+-ATP interactions substantially. Errors are computed with respect to estimates from vdW-inclusive density functional theory that we benchmark against "gold standard" CCSD(T) calculations and experiments. We will also present the ramifications of these improvements in local interactions on Mg2+-ATP binding free energies and binding modes in bulk water, and on complexation of Mg2+ and ATP with proteins.

Carbon tax acceptance in a polarized society: bridging the partisan divide over climate policy in the US

ABSTRACT Political polarization in the US hinders bipartisan support for carbon taxes. Polarization operates unconsciously via implicit biases (implicit level), but it also arises when individuals consciously reflect on their political identity and beliefs (explicit level). We conducted two survey experiments with online panels of the US population to examine how irreconcilable Democrats’ and Republicans’ views on carbon taxes are. Study 1 compared measurements from an Implicit Association Test (implicit level) and stated beliefs (explicit level). Results show carbon tax fairness perceptions were already polarized at implicit level, but the main divergence in attitudes occurred at explicit level. Since explicit attitudes are considered easier to influence than implicit ones, Study 2 tested the extent to which message framing could influence this deliberated—explicit—polarization. We used different frames targeted at Democrats and Republicans to convey the idea that carbon tax support does not threaten partisans’ political identity. Framings further polarized responses, increasing Democrats’ but reducing Republicans’ policy support. We discuss implications for climate policy communication in relation to navigating identity-based polarization. Policy Highlights Political polarization over climate policy in the US is driven by the interplay of affective and cognitive factors. Unconscious fairness perceptions about carbon taxes are already polarized. These differences amplify when Democrats and Republicans consciously report their perceptions. Identity-affirming framings that appeal to partisans’ concerns can influence carbon tax acceptance. Since Republicans may react negatively to climate policy communication, source credibility might be necessary to avoid backlash.

Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution.

Mononuclear polypyridine ruthenium (Ru) complexes can catalyze various reactions, including water splitting, and can also serve as photosensitizers in solar cells. Despite recent progress in their synthesis, accurately modeling their physicochemical properties, particularly in solution, remains challenging. Herein, we conduct a theoretical investigation of the structural and electronic properties of a mononuclear Ru-aqua polypyridine complex in aqueous solution, considering five of its possible oxidation/protonation states species: [RuII(H2O)(py)(bpy)2]2+, [RuII(OH)(py)(bpy)2]+, [RuIII(H2O)(py)(bpy)2]3+, [RuIII(OH)(py)(bpy)2]2+ and [RuIV(O)(py)(bpy)2]2+, where py = pyridine and bpy = 2,2'-bipyridine. At first, we investigate the impact of proton-coupled and non-coupled electron transfer reactions on the geometry and electronic structure of the complexes in vacuum and in solution, using an implicit solvent model. Then, using a sequential multiscale approach that combines quantum mechanics and molecular mechanics (S-QM/MM), we examine the explicit solvent effects on the electronic excitations of the complexes, and compare them with the experimental results. The complexes were synthesized, and their absorption spectra measured in aqueous solution. To accurately describe the QM interactions between the metal center and the aqueous ligand in the MM simulations, we developed new force field parameters for the Ru atom. We analyze the solvent structure around the complexes and account for its explicit influence on the polarization and electronic excitations of the complexes. Notably, accounting for the explicit solvent polarization effects of the first solvation shells is essential to correctly describe the energy of the electronic transitions, and the explicit treatment of the hydrogen bonds at the QM level in the excitation calculations improves the accuracy of the description of the metal-to-ligand charge-transfer bands. Transition density matrix analysis is used to characterize all electronic transitions in the visible and ultraviolet ranges according to their charge-transfer (CT) character. This study elucidates the electronic structure of those ruthenium polypyridyl complexes in aqueous solution and underscores the importance of precisely describing solvent effects, which can be achieved employing the S-QM/MM method.

Explicit Polarization in Coarse-Grained Simulations of Ionomer Melts

The structure and morphology of ionic aggregates in ionomer melts significantly influence their ion transport properties. Understanding the underlying mechanisms and relevant time scales of ion transport can facilitate design of viable ionomer materials as single-ion conductors for energy applications. Previous studies have characterized the ionic aggregate structure, morphology, and dynamics using non-polarizable coarse-grained molecular dynamics (CGMD) simulations. In this work, we examine the role of polarization in ionomer melts by explicitly incorporating Drude oscillators in CGMD simulations. We systematically study the structure and dynamics of pendant ionomers, focusing on the comparison to non-polarizable systems. Polarization within the ion clusters leads to less overall ion structuring. On the aggregate scale, less ion structuring yields smaller ionic aggregates. The extent to which the clusters are smaller delicately depends on the strength of the electrostatic interactions (the dielectric constant). Under certain conditions, we find that the time scale for free counterion diffusion does not depend on the morphology, unlike that in a non-polarizable model.

A Polarizable Cationic Dummy Metal Ion Model.

A novel locally polarizable multisite model based on the original cation dummy atom (CDA) model is described for molecular dynamics simulations of ions in condensed phases. Polarization effects are introduced by the electronegativity equalization model (EEM) method where charges on the metal ion and its dummy atoms can fluctuate to respond to the environment. This model includes explicit polarization and ion-induced interactions and can be coupled with nonpolarizable or polarizable water models, making it more transferable to simpler force fields. This approach allows us to enhance the original fixed charge CDA model where the charge distribution cannot adapt to the local solvent structure. To illustrate the new CDApol model, we examined properties of the Zn2+, Al3+, and Zr4+ ions in aqueous solution. The polarizable model and Lennard-Jones parameters were refined for octahedrally coordinated Zn2+, Al3+, and Zr4+ CDAs to reproduce thermodynamic and geometrical properties. Using this locally polarizable model, we were able to obtain the experimental hydration free energy, ion-oxygen distance, and coordination number coupled with the standard 12-6 Lennard-Jones model. This model can be used in myriad additional applications where local polarization and charge transfer is important.

Consistent Picture of Phosphate–Divalent Cation Binding from Models with Implicit and Explicit Electronic Polarization

The binding of divalent cations to the ubiquitous phosphate group is essential for a number of key biological processes, such as DNA compaction, RNA folding, or interactions of some proteins with membranes. Yet, probing their binding sites, modes, and associated binding free energy is a challenge for both experiments and simulations. In simulations, standard force fields strongly overestimate the interaction between phosphate groups and divalent cations. Here, we examine how different strategies to include electronic polarization effects in force fields─implicitly, through the use of scaled charges or pair-specific Lennard-Jones parameters, or explicitly, with the polarizable force fields Drude and AMOEBA─capture the interactions of a model phosphate compound, dimethyl phosphate, with calcium and magnesium divalent cations. We show that both implicit and explicit approaches, when carefully parameterized, are successful in capturing the overall binding free energy and that common trends emerge from the comparison of different simulation approaches. Overall, the binding is very moderate, slightly weaker for Ca2+ than Mg2+, and the solvent-shared ion pair is slightly more stable than the contact monodentate ion pair. The bidentate ion pair is higher in energy (or even fully unstable for Mg2+). Our results thus suggest practical ways to capture the divalent cations with biomolecular phosphate groups in complex biochemical systems. In particular, the computational efficiency of implicit models makes them ideally suited for large-scale simulations of biological assemblies, with improved accuracy compared to state-of-the-art fixed-charge force fields.

Shedding Light on Capillary-Based Backscattering Interferometry.

Capillary-based backscattering interferometry has been used extensively as a tool to measure molecular binding via interferometric refractive index sensing. Previous studies have analysed the fringe patterns created in the backscatter direction. However, polarisation effects, spatial chirps in the fringe pattern and the practical impact of various approximations, and assumptions in existing models are yet to be fully explored. Here, two independent ray tracing approaches are applied, analysed, contrasted, compared to experimental data, and improved upon by introducing explicit polarisation dependence. In doing so, the significance of the inner diameter, outer diameter, and material of the capillary to the resulting fringe pattern and subsequent analysis are elucidated for the first time. The inner diameter is shown to dictate the fringe pattern seen, and therefore, the effectiveness of any dechirping algorithm, demonstrating that current dechirping methods are only valid for a subset of capillary dimensions. Potential improvements are suggested in order to guide further research, increase sensitivity, and promote wider applicability.

Does Explicit Polarizability Improve Molecular Dynamics Predictions of Glass Transition Temperatures of Ionic Liquids?

Molecular dynamics simulations are used for predictions of the glass transition temperatures for a test set of five aprotic ionic liquids. Glass transitions are localized with the trend-shift method, analyzing volumetric and transport properties of bulk amorphous phases. A classical nonpolarizable all-atom OPLS force-field model developed by Canongia Lopes and Pádua (CL&P) is employed as a starting level of theory for all calculations. Alternative approaches of charge scaling and the Drude oscillator model, accounting for atomic polarizability either implicitly or explicitly, respectively, are used to investigate the sensitivity of the glass transition temperatures to induction effects. The former nonpolarizable model overestimates the glass transition temperature by tens of Kelvins (37 K on average). The charge-scaling technique yields a significant improvement, and the best estimations were achieved using polarizable simulations with the Drude model, which yielded an average deviation of 11 K. Although the volumetric data usually exhibit a lesser trend shift upon vitrification, their lower statistical uncertainty enables to predict the glass transition temperature with lower uncertainty than the ionic self-diffusivities, the temperature dependence of which is usually more scattered. Additional analyses of the simulated data were also performed, revealing that the Drude model predicts lower densities for most subcooled liquids but higher densities for the glasses than the original CL&P, and that the Drude model also invokes some longer-range organization of the subcooled liquid, greatly impacting the temperature trend of ionic self-diffusivities in the low-temperature region.

High-Dimensional Parameter Search Method to Determine Force Field Mixing Terms in Molecular Simulations.

Molecular dynamics (MD) force fields for lipids and ions are typically developed independently of one another. In simulations consisting of both lipids and ions, lipid-ion interaction energies are estimated using a predefined set of mixing rules for Lennard-Jones (LJ) interactions. This, however, does not guarantee their reliability. In fact, compared to the quantum mechanical reference data, Lorentz-Berthelot mixing rules substantially underestimate the binding energies of Na+ ions with small-molecule analogues of lipid headgroups, yielding errors on the order of 80 and 130 kJ/mol, respectively, for methyl acetate and diethyl phosphate. Previously, errors associated with mixing force fields have been reduced using approaches such as "NB-fix" in which LJ interactions are computed using explicit cross terms rather than those from mixing rules. Building on this idea, we derive explicit lipid-ion cross terms that also may implicitly include many-body cooperativity effects. Additionally, to account for the interdependency between cross terms, we optimize all cross terms simultaneously by performing high-dimensional searches using our ParOpt software. The cross terms we obtain reduce the errors due to mixing rules to below 10 kJ/mol. MD simulation of the lipid bilayer conducted using these optimized cross terms resolves the structural discrepancies between our previous simulations and small-angle X-ray and neutron scattering experiments. These results demonstrate that simulations of lipid bilayers with ions that are accurate up to structural data from scattering experiments can be performed without explicit polarization terms. However, it is worth noting that such NB-fix cross terms are not based on any physical principle; a polarizable lipid model would be more realistic and is still desired. Our approach is generic and can be applied to improve the accuracies of simulations employing mixed force fields.

CARNOT: a Fragment-Based Direct Molecular Dynamics and Virtual-Reality Simulation Package for Reactive Systems.

Traditionally, the study of reaction mechanisms of complex reaction systems such as combustion has been performed on an individual basis by optimizations of transition structure and minimum energy path or by reaction dynamics trajectory calculations for one elementary reaction at a time. It is effective, but time-consuming, whereas important and unexpected processes could have been missed. In this article, we present a direct molecular dynamics (DMD) approach and a virtual-reality simulation program, CARNOT, in which plausible chemical reactions are simulated simultaneously at finite temperature and pressure conditions. A key concept of the present ab initio molecular dynamics method is to partition a large, chemically reactive system into molecular fragments that can be adjusted on the fly of a DMD simulation. The theory represents an extension of the explicit polarization method to reactive events, called ReX-Pol. We propose a highest-and-lowest adapted-spin approximation to define the local spins of individual fragments, rather than treating the entire system by a delocalized wave function. Consequently, the present ab initio DMD can be applied to reactive systems consisting of an arbitrarily varying number of closed and open-shell fragments such as free radicals, zwitterions, and separate ions found in combustion and other reactions. A graph-data structure algorithm was incorporated in CARNOT for the analysis of reaction networks, suitable for reaction mechanism reduction. Employing the PW91 density functional theory and the 6-31+G(d) basis set, the capabilities of the CARNOT program were illustrated by a combustion reaction, consisting of 28 650 atoms, and by reaction network analysis that revealed a range of mechanistic and dynamical events. The method may be useful for applications to other types of complex reactions.

A Comparative Study of Spin Magnetic Moment, Spin Polarization and Curie Temperature of Heusler type Compounds (A<sub>2-X-Y</sub>Z<sub>y</sub>)Mnz (A = Ni, Pd, Pt And Z = Sb, Sn)

The Heusler type compounds (A2-x-yZy)MnZ (A = Ni, Pd, Pt; Z = Sb, Sn; x = 1, 0; and y = 0, antisite defects of Z atoms) are investigated to understand the induced magnetic properties. The structural phases C1b type half Heusler (x = 1, y = 0) compounds AMnZ and the corresponding L21 type full Heusler (x = y = 0) compounds A2MnZ and some disordered compounds (A1-yZy)MnZ and (A2-yZy)MnZ (y = 0.01, 0.05) were calculated using the Korringa-Kohn-Rostoker Green’s function method. The antisite doping of 1% (5%) Sb retained (suppressed) the half metallicity at (Ni1-ySby)MnSb, whereas the other compounds were found to be gapless in both spin directions. The density of states at the Fermi level exhibits the explicit spin polarization in the compounds. The net magnetic moments of the compounds are closer in their values, wherein the manganese atom is responsible for the major contribution to the magnetic moments, which is much larger than the partial moment of the other constituents. The Curie temperature (TC) of the ordered ferromagnetic compounds was estimated using the mean-field approximation. The TC higher than the room temperature was found for the ordered compounds, except for the cases of Pt2MnSb and Pt2MnSn. No literature value of TC has been reported yet for these two compounds. Calculated spin moments and TC agree well with the experimental results, where available. J. Bangladesh Acad. Sci. 45(2); 217-229: December 2021

Local-Field Effects in Linear Response Properties within a Polarizable Frozen Density Embedding Method

In this work, we present a polarizable frozen density embedding (FDE) method for calculating polarizabilities of coupled subsystems. The method (FDE-pol) combines a FDE method with an explicit polarization model such that the expensive freeze/thaw cycles can be bypassed, and approximate nonadditive kinetic potentials are avoided by enforcing external orthogonality between the subsystems. To describe the polarization of the frozen environment, we introduce a Hirshfeld partition-based density-dependent method for calculating the atomic polarizabilities of atoms in molecules, which alleviates the need to fit the atomic parameters to a specific system of interest or to a larger general set of molecules. We show that the Hirshfeld partition-based method predicts molecular polarizabilities close to the basis set limit, and thus, a single basis set-dependent scaling parameter can be introduced to improve the agreement against the reference polarizability data. To test the model, we characterized the uncoupled and coupled response of small interacting molecular complexes. Here, the coupled response properties include the perturbation of the frozen system due to the external perturbation which is ignored in the uncoupled response. We show that FDE-pol can accurately reproduce both the exact uncoupled polarizability and the coupled polarizabilities of the supermolecular systems. Using damped response theory, we also demonstrate that the coupled frequency-dependent polarizability can be described by including local field effects. The results emphasize the necessity of including local-field effects for describing the response properties of coupled subsystems, as well as the importance of accurate atomic polarizability models.