Electronic Polarization Effects Research Articles

INELASTIC LONGITUDINAL C6 ELECTRON SCATTERING FORM FACTORS IN Ti-50, (RESIDUAL INTERACTION CONSIDERATION)

The single orbit 1f7/2 has been adopted as a model space. The use of modern realistic M3Y effective nucleon- nucleon interaction with two sets of fitting parameters (Ried fitting (M3Y-P1), and Paris fitting (M3Y-P0)) beside the use of MSDI has been done as a residual interactions within the calculation of core polarization effects in Inelastic longitudinal electron scattering C6 form factor in Ti-50 within the framework of first order perturbation theory (microscopic theory) with 2ћω excitation energy coupling the core orbits to the higher configurations one across the model space at normal transition. Harmonic oscillator wave functions (H.O) has been adopted as a single particle wave functions in 1f7/2 and with the aid of F7MBZ model space 1f7/2 effective interaction to generate the model space wave functions. The present results have been compared with

Electronic polarization effects in core-level spectroscopy

Electronic polarization effects in core-level spectroscopy

Fenton-like membrane reactor assembled by electron polarization and defect engineering modifying Co3O4 spinel for flow-through removal of organic contaminants

The application of Fenton-like membrane reactors for water purification offers a promising solution to overcome technical challenges associated with catalyst recovery, reaction efficiency, and mass transfer typically encountered in heterogeneous batch reaction modes. This study presents a dual-modification strategy encompassing electron polarization and defect engineering to synthesize Al-doped and oxygen vacancies (OV)-enriched Co3O4 spinel catalysts (ACO-OV). This modification empowered ACO-OV with exceptional performance in activating peroxymonosulfate (PMS) for the removal of organic contaminants. Moreover, the ACO-OV@polyethersulfone (PES) membrane/PMS system achieved organic contaminant removal through filtration (with a reaction kinetic constant of 0.085 ms−1), demonstrating outstanding resistance to environmental interference and high operational stability. Mechanistic investigations revealed that the exceptional catalytic performance of this Fenton-like membrane reactor stemmed from the enrichment of reactants, exposure of reactive sites, and enhanced mass transfer within the confined space, leading to a higher availability of reactive species. Theoretical calculations were conducted to validate the beneficial intrinsic effects of electron polarization, defect engineering, and the confined space within the membrane reactor on PMS activation and organic contaminant removal. Notably, the ACO-OV@PES membrane/PMS system not only mineralized the targeted organic contaminants but also effectively mitigated their potential environmental risks. Overall, this work underscores the significant potential of the dual-modification strategy in designing spinel catalysts and Fenton-like membrane reactors for efficient organic contaminant removal.

Quantum chemical study on the catalytic debromination mechanism of brominated epoxy resins

The study employed Density Functional Theory (DFT) to investigate the catalytic debromination mechanism of brominated epoxy resins (BERs) by iron (Fe) and copper (Cu) catalysts. By introducing electric field (EF), intramolecular electron transfer and polarization effects on BERs debromination were explored and experimentally validated. Results indicated that the bond dissociation energy (BDE) of the C-Br bond was 312.27 kJ/mol without catalysis, while with Fe, Cu, and EF, it was 114.47 kJ/mol, 94.85 kJ/mol, and 292.59 kJ/mol, respectively, enhancing reactivity. EF parallel to the C-Br bond and oriented toward the C atom, altered electrostatic potential and dipole moment around C-Br bond, leading to 68.60% and 50.19% increment in electronic contribution difference and molecule polarity, respectively, thereby reducing the C-Br BDE. Fe and Cu facilitated electron transfers with BERs, inducing reactions between their negative electrostatic potentials and Br's positive potential, changing electron sharing, resulting in 19.87% and 12.11% increase in polarity, respectively, and further BDE reduction. Structural modifications by the EF and catalysts also intensified van der Waals forces with bromine atoms and decreased spatial hindrance, collectively making C-Br bond breakage easier. Experiments revealed the EF enhanced BERs' debromination efficiency but hindered Fe/Cu's catalysis at lower temperatures.

Nonaqueous Ion Pairing Exemplifies the Case for Including Electronic Polarization in Molecular Dynamics Simulations.

The inclusion of electronic polarization is of crucial importance in molecular simulations of systems containing charged moieties. When neglected, as often done in force field simulations, charge-charge interactions in solution may become severely overestimated, leading to unrealistically strong bindings of ions to biomolecules. The electronic continuum correction introduces electronic polarization in a mean-field way via scaling of charges by the reciprocal of the square root of the high-frequency dielectric constant of the solvent environment. Here, we use ab initio molecular dynamics simulations to quantify the effect of electronic polarization on pairs of like-charged ions in a model nonaqueous environment where electronic polarization is the only dielectric response. Our findings confirm the conceptual validity of this approach, underlining its applicability to complex aqueous biomolecular systems. Simultaneously, the results presented here justify the potential employment of weaker charge scaling factors in force field development.

Optimal Scheme to Achieve Energy Conservation in Induced Dipole Models.

Induced dipole models have proven to be effective tools for simulating electronic polarization effects in biochemical processes, yet their potential has been constrained by energy conservation issue, particularly when historical data is utilized for dipole prediction. This study identifies error outliers as the primary factor causing this failure of energy conservation and proposes a comprehensive scheme to overcome this limitation. Leveraging maximum relative errors as a convergence metric, our data demonstrates that energy conservation can be upheld even when using historical information for dipole predictions. Our study introduces the multi-order extrapolation method to quicken induction iteration and optimize the use of historical data, while also developing the preconditioned conjugate gradient with local iterations to refine the iteration process and effectively remove error outliers. This scheme further incorporates a "peek" step via Jacobi under-relaxation for optimal performance. Simulation evidence suggests that our proposed scheme can achieve energy convergence akin to that of point-charge models within a limited number of iterations, thus promising significant improvements in efficiency and accuracy.

Ionic and electronic polarization effects in horizontal hybrid perovskite device structures close to equilibrium.

The electrical response of hybrid perovskite devices carries a significant signature from mobile ionic defects, pointing to both opportunities and threats when it comes to functionality, performance and stability of these devices. Despite its importance, the interpretation of polarization effects due to the mixed ionic-electronic conducting nature of these materials and the quantification of their ionic conductivities still poses conceptual and practical challenges, even for the equilibrium situation. In this study, we address these questions and investigate the electrical response of horizontal devices based on methylammonium lead iodide (MAPI) close to equilibrium conditions. We discuss the interpretation of DC polarization and impedance spectroscopy measurements in the dark, based on calculated and fitted impedance spectra obtained using equivalent circuit models that account for the mixed conductivity of the perovskite and for the effect of device geometry. Our results show that, for horizontal structures with a gap width between the metal electrodes in the order of tens of microns, the polarization behavior of MAPI is well described by the charging of the mixed conductor/metal interface, suggesting a Debye length in the perovskite close to 1 nm. We highlight a signature in the impedance response at intermediate frequencies, which we assign to ionic diffusion in the plane parallel to the MAPI/contact interface. By comparing the experimental impedance results with calculated spectra for different circuit models, we discuss the potential role of multiple mobile ionic species and rule out a significant contribution from iodine exchange with the gas phase in the electrical response of MAPI close to equilibrium. This study helps to clarify the measurement and interpretation of mixed conductivity and polarization effects in hybrid perovskites with immediate relevance to the characterization and development of transistors, memristors and solar cells based on this class of materials as well as other mixed conductors.

A unique piezolyte mechanism of TMAO: Hydrophobic interactions under extreme pressure conditions.

We report a computer simulation study of the effect of trimethylamine N-oxide (TMAO) on the pressure stability of the hydrophobic contact interaction of two nonpolar α-helices. We found that TMAO counterbalanced the disruptive effect of pressure destabilization on account of an earlier reported electronic polarization effect that led to an increased TMAO dipole moment under compression of the solvent. This direct stabilization mechanism became ineffective when the dipole polarization of TMAO was not considered and was linked to nonspecific van der Waals interactions of TMAO with the nonpolar surfaces of the two helices, which became weaker as TMAO became stronger polarized at high pressure. The corresponding thermodynamic driving forces are discussed and should be generic for hydrophobic interactions under high pressure. The proposed mechanism suggests that TMAO stands out as a piezolyte among stabilizing osmolytes, potentially protecting biological assemblies formed by hydrophobic interactions under extreme pressure conditions.

Wavefunction frozen-density embedding with one-dimensional periodicity: Electronic polarization effects from local perturbations.

We report an approach to treat polarization effects in a one-dimensional (1D) environment using frozen-density embedding (FDE), suitable to compute response to electron loss or attachment as occurring in organic semiconductors during charge migration. The present work provides two key developments: (a) Local perturbations are computed avoiding an infinite repetition thereof and (b) a first-order equation-of-motion ansatz is used to compute polarization effects due to electron loss and attachment, ensuring an efficient calculation by avoiding open-shell calculations. In a first step, an unperturbed 1D molecular chain is equilibrated using FDE by translation of the center molecule. In a subsequent second step, long-range contributions are frozen and a local perturbation is introduced in the center subsystem. Freeze-thaw iterations are used to relax the electronic wavefunction of both the center subsystem and subsystems in an active region around the center subsystem, avoiding the need to translate the perturbation. The proposed scheme proves to be very efficient and allows for the calculation of charged tetraazaperopyrenes in 1D chains. Due to its efficiency, the new method is capable of providing wavefunction-based reference data relevant for electronic couplings in complex environments.

Force fields optimized against experimental data for large compound families using CombiFF: Validation considering non-target properties and polyfunctional compounds

The CombiFF scheme is a workflow for the automated calibration of force-field parameters against condensed-phase experimental data considering simultaneously entire classes of organic molecules. The main steps of this scheme are: (i) selection of a molecule family; (ii) enumeration of all isomers; (iii) query for experimental data; (iv) automatic construction of the molecular topologies; (v) iterative refinement of the force-field parameters considering the entire family. In two recent articles, CombiFF was applied to the design of GROMOS-compatible united-atom force fields for the saturated acyclic haloalkanes and for saturated acyclic compounds involving eight common chemical functional groups of oxygen and nitrogen. This calibration and the subsequent initial validation involved two limitations: (i) the experimental data considered was restricted to values for the pure-liquid density ρliq and the vaporization enthalpy ΔHvap of the compounds; (ii) beyond monofunctional compounds, the training set only involved homo-polyhaloalkanes (possibly mixing halogen types) in the first study, and homo-polyfunctional compounds of the considered oxygen or nitrogen functional groups (no mixing of different group types) in the second one. The goal of this article is to further test the accuracy of CombiFF-generated force fields by extending the validation to: (i) nine additional properties that were not used as optimization targets (pure-liquid thermodynamic, dielectric and transport properties, as well as solvation properties); (ii) hetero-polyfunctional molecules that were not included in the calibration and initial validation sets. The results for the nine additional properties show good agreement with experiment, except for the shear viscosity and the dielectric permittivity. There, larger discrepancies are observed, likely due to the united-atom representation adopted for the aliphatic groups and to the implicit treatment of electronic polarization effects. The results for the hetero-polyfunctional molecules also show reasonable agreement with experiment in terms of the monitored properties.

Internal Electric Field-Induced Formation of Exotic Linear Acetonitrile Chains.

The application of external electric and magnetic fields is a powerful tool for aligning molecules in a controlled way, if the thermal fluctuations are small. Here we demonstrate that the same holds for internal electric fields in a molecular cluster. The electric field of a single molecular dipole, HCl, is used to manipulate the aggregation mechanism of subsequently added acetonitrile molecules. As a result, we could form exotic linear acetonitrile (CH3CN) chains at 0.37 K, as confirmed by infrared spectroscopy in superfluid helium nanodroplets. These linear chains are not observed in the absence of HCl and can be observed only when the internal electric field created by an HCl molecule is present. The accompanying simulations provide mechanistic insights into steric control, explain the selectivity of the process, and show that non-additive electronic polarization effects systematically enhance the dipole moment of these linear chains. Thus, adding more CH3CN monomers even supports further quasi-linear chain growth.

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.

Nearest-Neighbor dsDNA Stability Analysis Using Alchemical Free-Energy Simulations.

The thermodynamic stability of double-stranded (ds)DNA depends on its sequence. It is influenced by the base pairing and stacking with neighboring bases along DNA molecules. Semiempirical schemes are available that allow us to predict the thermodynamic stability of DNA sequences based on empirically derived nearest-neighbor contributions of base pairs formed in the context of all possible nearest-neighbor base pairs. Current molecular dynamics (MD) simulations allow one to simulate the dynamics of DNA molecules in good agreement with experimentally obtained structures and available data on conformational flexibility. However, the suitability of current force field methods to reproduce dsDNA stability and its sequence dependence has been much less well tested. We have employed alchemical free-energy simulations of whole base pair transversions in dsDNA and in unbound single-stranded partner molecules. Such transversions change the sequence context but not the nucleotide content or base pairing in dsDNA and allow a direct comparison with the empirical nearest-neighbor dsDNA stability model. For the alchemical free-energy changes in the unbound single-stranded (ss)DNA partner molecules, we tested different setups assuming either complete unstacking or unrestrained simulations with partial stacking in the unbound ssDNA. The free-energy simulations predicted nearest-neighbor effects of similar magnitude, as observed experimentally but showed overall limited correlation with experimental data. An inaccurate description of stacking interactions and other possible reasons such as the neglect of electronic polarization effects are discussed. The results indicate the need to improve the realistic description of stacking interactions in current molecular mechanic force fields.

Deep Neural Network Model to Predict the Electrostatic Parameters in the Polarizable Classical Drude Oscillator Force Field.

The Drude polarizable force field (FF) captures electronic polarization effects via auxiliary Drude particles that are attached to non-hydrogen atoms, distinguishing it from commonly used additive FFs that rely on fixed charges. The Drude FF currently includes parameters for biomolecules such as proteins, nucleic acids, lipids, and carbohydrates and small-molecule representative of those classes of molecules as well as a range of atomic ions. Extension of the Drude FF to novel small druglike molecules is challenging as it requires the assignment of partial charges, atomic polarizabilities, and Thole scaling factors. In the present article, deep neural network (DNN) models are trained on quantum mechanical (QM)-based partial charges and atomic polarizabilities along with Thole scale factors trained to target QM molecular dipole moments and polarizabilities. Training of the DNN model used a collection of 39 421 molecules with molecular weights up to 200 Da and containing H, C, N, O, P, S, F, Cl, Br, or I atoms. The DNN model utilizes bond connectivity, including 1,2, 1,3, 1,4, and 1,5 terms and distances of Drude FF atom types as the feature vector to build the model, allowing it to capture both local and nonlocal effects in the molecules. Novel methods have been developed to determine restrained electrostatic potential (RESP) charges on atoms and external points representing lone pairs and to determine Thole scale factors, which have no QM analogue. A penalty scheme is devised as a performance predictor of the trained model. Validation studies show that these DNN models can precisely predict molecular dipole and polarizabilities of Food and Drug Administration (FDA)-approved drugs compared to reference MP2 calculations. The availability of the DNN model allowing for the rapid estimation of the Drude electrostatic parameters will facilitate its applicability to a wider range of molecular species.

Electronic polarization effects on membrane translocation of anti-cancer drugs.

Free-energy calculations are crucial for investigating biomolecular interactions. However, in theoretical studies, the neglect of electronic polarization can reduce predictive capabilities, specifically for free-energy calculations. To effectively mimick polarization, we explore a Charge Switching (CS) model, aiming to narrow the gap between computational and experimental results. The model requires quantum-level partial charge calculations of the molecule in different environments, combined with atomistic MD simulations. Studying three different anti-cancer drug molecules with three different phospholipid membranes, we show that the method significantly improves agreement with available experimental data. In contrast, using conventional fixed charge atomistic methods, qualitative discrepancies with experiments are observed, and we show that neglecting polarization may lead to an unphysical free energy sign inversion. While the CS method is here applied to anti-cancer drug-membrane translocation, it could be used more generally to study processes considering solvent effects.

Photon polarization effects in polarized electron–positron pair production in a strong laser field

Deep understanding of the impact of photon polarization on pair production is essential for the efficient generation of laser-driven polarized positron beams and demands a complete description of polarization effects in strong-field QED processes. Employing fully polarization-resolved Monte Carlo simulations, we investigate correlated photon and electron (positron) polarization effects in the multiphoton Breit–Wheeler pair production process during the interaction of an ultrarelativistic electron beam with a counterpropagating elliptically polarized laser pulse. We show that the polarization of e−e+ pairs is degraded by 35% when the polarization of the intermediate photon is resolved, accompanied by an ∼13% decrease in the pair yield. Moreover, in this case, the polarization direction of energetic positrons at small deflection angles can even be reversed when high-energy photons with polarization parallel to the laser electric field are involved.

Mixed Metal Oxide Electrodes and the Chlorine Evolution Reaction

The chlorine evolution reaction (CER) has practical applications in the chlor-alkali industry and electrochemical wastewater treatment. Efficient, stable, and cost-effective electrodes are critical for energy efficient chlorine production, water disinfection, and wastewater treatment. These practical applications require an in-depth understanding of the catalytic mechanism of chlorine evolution, the need for lower-cost electrode materials, and improvements in electrode design at the atomic scale. Herein, we examine factors controlling activity, selectivity, and stability of alternative CER electrodes and provide mechanistic insights for achieving improvements in performance and durability. Steric effects of crystal structure and intermetallic electron polarization provide insights for understanding and tuning the electrode activity and selectivity. Additional insight into electrode deactivation mechanisms was gained by employing model material systems under controlled conditions. Herein, we explore viable strategies for the development of more efficient noble-metal-free CER electrodes for use in a variety of practical applications.

Structural, dielectric, impedance and ferroelectric properties of lead-free Bi(Fe0.85Dy0.15)O3 ceramic

Nowadays, several research groups are extensively trying to develop by synthesizing and characterizing single/co-doped single-phase bismuth ferrite (BFO) in order to get a highly efficient eco-friendly multifunctional devices. In this process, this report is an attempt to provide the detailed studies of structural, dielectric, impedance and ferroelectric properties of Bi(Fe0.85Dy0.15)O3 ceramic fabricated via the solid-state reaction method. Analysis of X-ray diffraction (XRD) data confirms a single phase of orthorhombic symmetry. The average crystallite (particle) size is found to be in the order of ~ 41 nm. The field emission scanning electron microscopy (FE-SEM) spectrum shows a homogeneous grain distribution of the sample. The elemental composition examined by means of energy dispersive X-ray spectroscopy (EDXS) shows the existence of constituent elements of the sample. The electrical measurements and analysis, carried out using a computer-controlled phase sensitive multimeter (PSM) in a frequency range of 1 kHz–1 MHz at different sets of temperature (25–325 °C), provide many interesting features to explain further conduction mechanism. The dielectric analysis exhibits high value of dielectric constant (ɛr) and small value of dielectric loss (tanδ). Due to the effect of electronic and space charge polarization, the ɛr value falls with an increasing frequency. The frequency–temperature dependence of impedance and electrical modulus analysis reveals the presence of semiconductor nature and non-Debye type of relaxation process in the sample. The analysis of ac-conductivity (σac) with respect to frequency and temperature obeys the universal Jonscher’s power law. The electric polarization study shows an enhancement in ferroelectric property of the material. Hence, based on the significant enhancement in electrical and ferroelectric properties of the Bi(Fe0.85Dy0.15)O3 material, the material may be considered for some applications.

Methylguanidinium at the Air/Water Interface: A Simulation Study with the Drude Polarizable Force Field.

Methylguanidinium is an important molecular ion, which also serves as the model compound for the arginine side chain. We studied the structure and dynamics of the methylguanidium ion at the air/water interface by molecular dynamics simulations employing the Drude polarizable force field. We found out that methylguanidinium accumulated at the interface, with a majority adopting tilted conformations. We also demonstrated that methylguanidinium and guanidinium ions had different preference toward the air/water interface. Detailed analysis of induced dipole moments showed how ions adjusted their charge distribution at the interface and revealed how the anisotropy in molecular polarizability impacted the orientation of molecular ions. Our results illustrate the importance of explicitly including the electronic polarization effects in modeling interfacial properties.

Charge Energetics and Electronic Level Changes At the Copper(II) Phthalocyanine/Fullerene Junction Upon Photoexcitation.

Energy offset at the donor (D)/acceptor (A) interface plays an important role in charge separation in organic photovoltaics. Its magnitude determines the charge separation process under illumination. Extensive studies have been carried out for elucidating the charge transfer (CT) process at different D/A junctions. These works lead to two different views: upon photoexcitation, energies would be (1) consumed in molecular polarization and orientation such that those opposite charges would overcome mutual Coulombic attractive potential at the interface and (2) spent on promoting charges to high-lying delocalized energy states (i.e., hot states), which is necessarily important prior to charge separation. Under these two scheme of studies, the electronic structures and the charge behaviors at the D/A interface should be different under photoexcitation, yet there is so far no direct experimental approach for probing the changes in electronics structures (i.e., Fermi level, vacuum level, frontier molecular orbitals, etc.) upon photoexcitation. Herein, a modified photoelectron spectroscopy (PES) system with an additional solar simulator is used to study the charge distributions and electronic interactions for a standard D/A heterojunction (i.e., copper phthalocyanine (CuPc)/ fullerene (C60)) under photoexcitation. CT states formed as a result of photon energy transfer at the CuPc/C60 junction. Subsequent superpositions of charge transfer and electron polarization effects increase the D/A energy level offsets from 0.75 (ground state measured in the dark) to 1.07 eV (high-lying state measured upon illumination). We showed that there is excess energy consumed for a subtle change in the energy level alignment of the CuPc/C60 junction under illumination, suggesting a new insight for the energy loss mechanism during the photocharge generation processes.