Electronic and Transport Properties of InSe/PtTe2 van der Waals Heterostructure.

Two-dimensional (2D) InSe and PtTe2 have drawn extensive attention due to their intriguing properties. However, the InSe monolayer is an indirect bandgap semiconductor with a low hole mobility. van der Waals (vdW) heterostructures produce interesting electronic and optoelectronic properties beyond the existing 2D materials and endow totally new device functions. Herein, we theoretically investigated the electronic structures, transport behaviors, and electric field tuning effects of the InSe/PtTe2 vdW heterostructures. The calculated results show that the direct bandgap type-II vdW heterostructures can be realized by regulating the stacking configurations of heterostructures. By applying an external electric field, the band alignment and bandgap of the heterostructures can also be flexibly modulated. Particularly, the hole mobility of the heterostructures is improved by 2 orders of magnitude to ∼103 cm2 V-1 s-1, which overcomes the intrinsic disadvantage of the InSe monolayer. The InSe/PtTe2 vdW heterostructures have great potential applications in developing novel optoelectronic devices.

Cyclometalated gold(III)-hydride under oriented external electric fields: a new strategy to modulate its reactivity?

Selected gold complexes have been regarded as promising anti-cancer agents because they can bind with protein targets containing thiol or selenol moieties, but their clinical applications were hindered by the unbiased binding towards off-target thiol-proteins. Recently, a novel gold(III)-hydride complex (abbreviated as 1) with visible light-induced thiol reactivity has been reported as potent photo-activated anticancer agents (Angew. Chem. Int. Ed., 2020, 132, 11139). To explore new strategies to stimuli this potential antitumor drug, the effect of oriented external electric fields (OEEFs) on its geometric structure, electronic properties, and chemical reactivity was systematically investigated. Results reveal that imposing external electric fields along the Au-H bond of 1 can effectively activate this bond, which is conducive to its dissociation and the binding of Au site to potential targets. Hence, this study provides a new OEEF-strategy to activate this reported gold(III)-hydride, revealing its potential application in electrochemical therapy. We anticipate this work could promote the development of more electric field-activated anticancer agents. However, further experimental research should be conducted to verify the conclusions obtained in this work.

Optimal Oriented External Electric Fields to Trigger a Barrierless Oxaphosphetane Ring Opening Step of the Wittig Reaction.

The Wittig reaction is one of the most important processes in organic chemistry for the asymmetric synthesis of olefinic compounds. In view of the increasingly acknowledged potentiality of the electric fields in promoting reactions, here we will consider the effect of the oriented external electric field (OEEF) on the second step of Wittig reaction (i. e. the ring opening oxaphosphetane) in a model system for non-stabilized ylides. In particular, we have determined the optimal direction and strength of the electric field that should be applied to annihilate the reaction barrier of the ring opening through the polarizable molecular electric dipole (PMED) model that we have recently developed. We conclude that the application of the optimal external electric field for the oxaphosphetane ring opening favours a Bestmann-like mechanism.

Effect of External Electric Field on Nitrogen Activation on a Trimetal Cluster.

Efficient nitrogen (N2) fixation and activation under mild conditions are crucial for modern society. External electric fields (Felectric) can significantly affect N2 activation. In this work, the effect of Felectric on N2 activation by Nb3 clusters supported in a sumanene bowl was studied by density functional theory calculations. Four typical systems at different stages of N-N activation were studied, including two intermediates and two transition states. The impact of Felectric on various properties related to N2 activation was investigated, including the N-N bond length, overlap population density of states (OPDOS), total energy of the system, adsorption energy of N2, decomposition of energy changes, and electron transfer. The sumanene not only functions as a support and protective substrate, but also serves as a donor or acceptor under different Felectric conditions. Negative Felectric is beneficial to N-N bond activation because it promotes electron transfer to the N-N region and improves the d-π* orbital hybridization between metals and N2 in the activation process. Positive Felectric improves d-π* orbital hybridization only when the N-N is nearly dissociated. The microscopic mechanism of Felectric's effects provides insight into N2 activation and theoretical guidance for the design of catalytic reaction conditions for nitrogen reduction reactions (NRR).

Finite Temperature String with Order Parameter as Collective Variables for Molecular Crystal: A Case of Polymorphic Transformation of TNT under External Electric Field.

An external electric field is an effective tool to induce the polymorphic transformation of molecular crystals, which is important practically in the chemical, material, and energy storage industries. However, the understanding of this mechanism is poor at the molecular level. In this work, two types of order parameters (OPs) were constructed for the molecular crystal based on the intermolecular distance, bond orientation, and molecular orientation. Using the K-means clustering algorithm for the sampling of OPs based on the Euclidean distance and density weight, the polymorphic transformation of TNT was investigated using a finite temperature string (FTS) under external electric fields. The potential of mean force (PMF) was obtained, and the essence of the polymorphic transformation between o-TNT and m-TNT was revealed, which verified the effectiveness of the FTS method based on K-means clustering to OPs. The differences in PMFs between the o-TNT and transition state were decreased under external electric fields in comparison with those in no field. The fields parallel to the c-axis obviously affected the difference in PMF, and the relationship between the changes in PMFs and field strengths was found. Although the external electric field did not promote the convergence, the time of the polymorphic transformation was reduced under the external electric field in comparison to its absence. Moreover, under the external electric field, the polymorphic transformation from o-TNT to m-TNT occurred while that from m-TNT to o-TNT was prevented, which was explained by the dipole moment of molecule, relative permittivity, chemical potential difference, nucleation work and nucleation rate. This confirmed that the polymorphic transformation orientation of the molecular crystal could be controlled by the external electric field. This work provides an effective way to explore the polymorphic transformation of the molecular crystals at a molecular level, and it is useful to control the production process and improve the performance of energetic materials by using the external electric fields.

Stationary External Electric Field-Mimicking the Solvent Effect on the Ground-State Tautomerism and Excited-State Proton Transfer in 8-(Benzo[d]thiazol-2-yl)quinolin-7-ol.

The effect of the external electric field on the ground-state tautomerism in 8-(benzo[d]thiazol-2-yl)quinolin-7-ol has been studied by using density functional theory. The compound exists as an enol tautomer (off state) and under the influence of the external electric field a long-range intramolecular proton transfer can occur, placing the tautomeric proton at the quinolyl nitrogen atom (on state). This is a result of the much higher dipole moment of the end keto tautomer and indicates that the external electric field can be used to mimic the implicit solvent effect in tautomeric systems. In the excited state, the further stabilization of the most polar on state leads to a situation when the excited-state intramolecular proton transfer becomes impossible, limiting the intramolecular rotation to the conical intersection region.

Experimental and Theoretical Investigation of External Electric-Field-Induced Crystallization of TKX-50 from Solution by Finite-Temperature String with Order Parameters as Collective Variables for Ionic Crystals.

External electric fields are an effective tool to induce phase transformations. The crystallization of ionic crystals from solution is a common phase transformation. However, understanding of mechanisms is poor at the molecular level. In this work, we carried out an experimental and theoretical investigation of the external electric-field-induced crystallization of TKX-50 from saturated formic acid solution by finite-temperature string (FTS) with order parameters (OPs) as collective variables for ionic crystals. The minimum-free-energy path was sketched by the string method in collective variables. The results show that the K-means clustering algorithm based on Euclidean distance and density weights can be used for enhanced sampling of the OPs in external electric-field-induced crystallization of ionic crystal from solution, which improves the conventional FTS. The crystallization from solution is a process of surface-mediated nucleation. The external electric field can accelerate the evolution of the string and decrease the difference in the potential of mean forces between the crystal and the transition state. Due to the significant change in OPs induced by the external electric field in nucleation, the crystalline quality was enhanced, which explains the experimental results that the external electric field enhanced the density, detonation velocity, and detonation pressure of TKX-50. This work provides an effective way to explore the crystallization of ionic crystals from solution at the molecular level, and it is useful for improving the properties of ionic crystal explosives by using external electric fields.

Methane Activation by [AlFeO3 ]+ : the Hidden Spin Selectivity.

The performance of heteronuclear cluster [AlFeO3 ]+ in activating methane has been explored by a combination of high-level quantum chemical calculations with gas-phase experiments. At room temperature, [AlFeO3 ]+ is a mixture of 7 [AlFeO3 ]+ and 5 [AlFeO3 ]+ , in which two states lead to different reactivity and chemoselectivity for methane activation. While hydrogen extracted from methane is the only product channel for the 7 [AlFeO3 ]+ /CH4 couple, 5 [AlFeO3 ]+ is able to convert this substrate to formaldehyde. In addition, the introduction of an external electric field may regulate the reactivity and product selectivity. The interesting doping effect of Fe and the associated electronic origins are discussed, which may guide one on the design of Fe-involved catalyst for methane conversion.

Strong External Electric Fields Reduce Explosive Sensitivity: A Theoretical Investigation into the Reaction Selectivity in NH2NO2∙∙∙NH3.

Controlling the selectivity of a detonation initiation reaction of explosive is essential to reduce sensitivity, and it seems impossible to reduce it by strengthening the external electric field. To verify this, the effects of external electric fields on the initiation reactions in NH2NO2∙∙∙NH3, a model system of the nitroamine explosive with alkaline additive, were investigated at the MP2/6-311++G(2d,p) and CCSD(T)/6-311++G(2d,p) levels. The concerted effect in the intermolecular hydrogen exchange is characterized by an index of the imaginary vibrations. Due to the weakened concerted effects by the electric field along the -x-direction opposite to the "reaction axis", the dominant reaction changes from the intermolecular hydrogen exchange to 1,3-intramolecular hydrogen transference with the increase in the field strengths. Furthermore, the stronger the field strengths, the higher the barrier heights become, indicating the lower sensitivities. Therefore, by increasing the field strength and adjusting the orientation between the field and "reaction axis", not only can the reaction selectivity be controlled, but the sensitivity can also be reduced, in particular under a super-strong field. Thus, a traditional concept, in which the explosive is dangerous under the super-strong external electric field, is theoretically broken. Compared to the neutral medium, a low sensitivity of the explosive with alkaline can be achieved under the stronger field. Employing atoms in molecules, reduced density gradient, and surface electrostatic potentials, the origin of the reaction selectivity and sensitivity change is revealed. This work provides a new idea for the technical improvement regarding adding the external electric field into the explosive system.

Model of B9N9 Response under External Electric Field: Geometry, Electronic Properties, Reaction Activity.

In this paper, we performed the ωB97XD/def2-TZVP method with a density functional theory study on the boron-nitrogen (BN) analogues of cyclo[18]carbon. The geometric structure, polarization properties, and excitation effect were calculated in the presence of an external electric field (EEF). Furthermore, the dual descriptor and Fukui function matrices were employed to predict the tendency towards the electrophilic or nucleophilic reactions of B9N9 under varying EEF strengths. The results show that the application of an EEF will cause the cyclic structure of B9N9 to be considerably distorted towards an elliptical geometry, the polarization to increase, and the reactivity of B9N9 to enhance with the increase in the EEF strength. This is of great significance for further experimental exploration into the catalytic properties of BN fullerenes.

Harnessing Greenhouse Gases Absorption by Doped Fullerenes with Externally Oriented Electric Field.

In this work, a theoretical investigation of the effects caused by the doping of C20 with silicon (Si) atom as well as the adsorption of CO, CO2 and N2 gases to C20 and C19Si fullerenes was carried out. In concordance with previous studies, it was found that the choice of the doping site can control the structural, electronic, and energetic characteristics of the C19Si system. The ability of C20 and C19Si to adsorb CO, CO2 and N2 gas molecules was evaluated. In order to modulate the process of adsorption of these chemical species to C19Si, an externally oriented electric field was included in the theoretical calculations. It was observed that C19Si is highly selective with respect to CO adsorption. Upon the increase of the electric field intensity the adsorption energy was magnified correspondingly and that the interaction between CO and C19Si changes in nature from a physical adsorption to a partial covalent character interaction.

How Oriented External Electric Fields Modulate Reactivity.

A judiciously oriented external electric field (OEEF) can catalyze a wide range of reactions and can even induce endo/exo stereoselectivity of cycloaddition reactions. The Diels-Alder reaction between cyclopentadiene and maleic anhydride is studied by using quantitative activation strain and Kohn-Sham molecular orbital theory to pinpoint the origin of these catalytic and stereoselective effects. Our quantitative model reveals that an OEEF along the reaction axis induces an enhanced electrostatic and orbital interaction between the reactants, which in turn lowers the reaction barrier. The stronger electrostatic interaction originates from an increased electron density difference between the reactants at the reactive center, and the enhanced orbital interaction arises from the promoted normal electron demand donor-acceptor interaction driven by the OEEF. An OEEF perpendicular to the plane of the reaction axis solely stabilizes the exo pathway of this reaction, whereas the endo pathway remains unaltered and efficiently steers the endo/exo stereoselectivity. The influence of the OEEF on the inverse electron demand Diels-Alder reaction is also investigated; unexpectedly, it inhibits the reaction, as the electric field now suppresses the critical inverse electron demand donor-acceptor interaction.

1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution.

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its 31P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this 31P chemical shift. This approach has been tested on a variety of the metals of groups 8-12 and molecular structures. General recommendations for appropriate basis sets are reported.

Modeling of Solute-Solvent Interactions Using an External Electric Field-From Tautomeric Equilibrium in Nonpolar Solvents to the Dissociation of Alkali Metal Halides.

An implicit account of the solvent effect can be carried out using traditional static quantum chemistry calculations by applying an external electric field to the studied molecular system. This approach allows one to distinguish between the effects of the macroscopic reaction field of the solvent and specific solute-solvent interactions. In this study, we report on the dependence of the simulation results on the use of the polarizable continuum approximation and on the importance of the solvent effect in nonpolar solvents. The latter was demonstrated using experimental data on tautomeric equilibria between the pyridone and hydroxypyridine forms of 2,6-di-tert-butyl-4-hydroxy-pyridine in cyclohexane and chloroform.

TITAN: A Code for Modeling and Generating Electric Fields-Features and Applications to Enzymatic Reactivity.

We present here a versatile computational code named "elecTric fIeld generaTion And maNipulation (TITAN)," capable of generating various types of external electric fields, as well as quantifying the local (or intrinsic) electric fields present in proteins and other biological systems according to Coulomb's Law. The generated electric fields can be coupled with quantum mechanics (QM), molecular mechanics (MM), QM/MM, and molecular dynamics calculations in most available software packages. The capabilities of the TITAN code are illustrated throughout the text with the help of examples. We end by presenting an application, in which the effects of the local electric field on the hydrogen transfer reaction in cytochrome P450 OleTJE enzyme and the modifications induced by the application of an oriented external electric field are examined. We find that the protein matrix in P450 OleTJE acts as a moderate catalyst and that orienting an external electric field along the Fe─O bond of compound I has the biggest impact on the reaction barrier. The induced catalysis/inhibition correlates with the calculated spin density on the O-atom. © 2019 Wiley Periodicals, Inc.

Effect of Transmembrane Electric Field on GM1 Containing DMPC-Cholesterol Monolayer: A Computational Study.

Transmembrane electric potentials and membrane curvature have always provided pathways to mediate different cellular processes. We present results of molecular dynamics (MD) simulations of lipid monolayer composed of 1, 2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and cholesterol (CHOL) under a transverse electric field to monitor the effect of electric field on membrane containing ganglioside monosialo 1 (GM1). Four systems were studied with membrane monolayer in the presence and absence of GM1 with and without applying electric field along the normal of the monolayer. The applied transmembrane electric field was 0.4 mV/Å which corresponds to the action potential of animal cell. Our results indicate that the electric field induces a considerable lateral stress on the monolayer in the presence of GM1, which is evident from the lateral pressure profiles. It was found that due to the application of electric field major perturbation was caused to the system containing GM1, manifested by the bending of the monolayer. We believe this study provides correlation between electric field and spontaneous membrane bending, specially based on the membrane composition. The consequences of these MD simulations provide considerable insights to different biological phenomenon and lipid membrane models.

Adduct under Field-A Qualitative Approach to Account for Solvent Effect on Hydrogen Bonding.

The location of a mobile proton in acid-base complexes in aprotic solvents can be predicted using a simplified Adduct under Field (AuF) approach, where solute-solvent effects on the geometry of hydrogen bond are simulated using a fictitious external electric field. The parameters of the field have been estimated using experimental data on acid-base complexes in CDF3/CDClF2. With some limitations, they can be applied to the chemically similar CHCl3 and CH2Cl2. The obtained data indicate that the solute-solvent effects are critically important regardless of the type of complexes. The temperature dependences of the strength and fluctuation rate of the field explain the behavior of experimentally measured parameters.

A greener catalyst for hydroboration of imines-external electric field modify the reaction mechanism.

Usually, an extra catalyst (for example, the transition metal complexes) need to be used in catalyzing hydroboration, which involved the cost, environment, and so forth. Here, a greener and controllable catalyst-external electric field (EEF) was used to study its effect on hydroboration of N-(4-methylbenzyl)aniline (PhN═CHPhMe) with pinacolboane (HBPin). The results demonstrated that EEF could affect the barrier heights of both two pathways of this reaction. More significantly, flipping the direction of EEF could modify the reaction mechanism to induce a dominant inverse hydroboration at some field strength. That is to say, oriented EEF is a controlling switch for the anti- or Markovnikov hydroboration reaction of imines. This investigation is meaningful for the exploration of greener catalyst for chemistry reaction and guide a new method for the Markovnikov hydroboration addition. © 2019 Wiley Periodicals, Inc.

Theoretical study of methane adsorption and C─H bond activation over Fe-embedded graphene: Effect of external electric field.

The effect of an external electric field (EF) on the methane adsorption and its activation on iron-embedded graphene (Fe-GPs) are investigated by using the M06-L density functional method. The EF is applied in the perpendicular direction to the graphene in the range of -0.015 to +0.015 a.u. with the interval of 0.005 a.u. The effects of EF on the adsorption, transition state and product complexes of the methane activation reaction are revealed. The binding energies of methane on Fe site in Fe-GPs are increased from -12.9 to -15.3, -18.1 and -21.5 kcal/mol for the negative EF of -0.005, -0.010 and -0.015, respectively. By applying positive EF, the activation barriers for methane activation are reduced in range of 3-8 kcal/mol (around 12-31%) and the reaction energies are more exothermic. The positive EF kinetically favors the reaction compared to the system without EF. The adsorption and activation of methane on Fe-GPs can be easily tuned by adjusting the external electric field for various applications. © 2019 Wiley Periodicals, Inc.

Simulation of the effect of an external GHz electric field on the potential energy profile of Ca2+ ions in the selectivity filter of the CaV Ab channel.

CaV channels are transmembrane proteins that mediate and regulate ion fluxes across cell membranes, and they are activated in response to action potentials to allow Ca2+ influx. Since ion channels are composed of charge or polar groups, an external alternating electric field may affect the ion-selective membrane transport and the performance of the channel. In this article, we have investigated the effect of an external GHz electric field on the dynamics of calcium ions in the selectivity filter of the CaV Ab channel. Molecular dynamics (MD) simulations and the potential of mean force (PMF) calculations were carried out, via the umbrella sampling method, to determine the free energy profile of Ca2+ ions in the CaV Ab channels in presence and absence of an external field. Exposing CaV Ab channel to 1, 2, 3, 4, and 5 GHz electric fields increases the depth of the potential energy well and this may result in an increase in the affinity and strength of Ca2+ ions to binding sites in the selectivity filter the channel. This increase of strength of Ca2+ ions binding in the selectivity filter may interrupt the mechanism of Ca2+ ion conduction, and leads to a reduction of Ca2+ ion permeation through the CaV Ab channel.