scholarly journals A Bond Bundle Case Study of Diels-Alder Catalysis Using Oriented Electric Fields

Author(s):  
Timothy Wilson ◽  
Mark Eberhart

Bond bundles are chemical bonding regions, analogous to Bader atoms, uniquely defined according to the topology of the gradient bundle condensed charge density, itself obtained by a process of infinitesimal partitioning of the three-dimensional charge density into differential zero-flux surface bounded regions. Here we use bond bundle analysis to investigate the response of the charge density to an oriented electric field in general, and the catalytic effect of such a field on Diels-Alder reactions in particular, which in this case is found to catalyze by allowing the transition state valance bond bundle configuration to be achieved earlier along the reaction pathway. Using precise numerical values, we arrive at the conclusion that chemical reactions and electric field catalysis can be understood in terms of intra-atomic charge density redistribution, i.e., that charge shifts within more so than between atoms account for the making and breaking of bonds.

2021 ◽  
Author(s):  
Timothy Wilson ◽  
Mark Eberhart

Bond bundles are chemical bonding regions, analogous to Bader atoms, uniquely defined according to the topology of the gradient bundle condensed charge density, itself obtained by a process of infinitesimal partitioning of the three-dimensional charge density into differential zero-flux surface bounded regions. Here we use bond bundle analysis to investigate the response of the charge density to an oriented electric field in general, and the catalytic effect of such a field on Diels-Alder reactions in particular, which in this case is found to catalyze by allowing the transition state valance bond bundle configuration to be achieved earlier along the reaction pathway. Using precise numerical values, we arrive at the conclusion that chemical reactions and electric field catalysis can be understood in terms of intra-atomic charge density redistribution, i.e., that charge shifts within more so than between atoms account for the making and breaking of bonds.


2010 ◽  
Vol 6 (1) ◽  
pp. 31 ◽  
Author(s):  
Cristina Peratta ◽  
Andres Peratta ◽  
Dragan Poljak

The paper introduces a three dimensional multidomainboundary element model of a pregnant woman and foetus for the analysis of exposure to high voltage extremely low frequency electric fields. The definition of the differentphysical and geometrical properties of the relevant tissues is established according to medical information available in existing literature. The model takes into account changes in geometry, body mass, body fat, and overall chemical composition in the body which influence the electrical properties, throughout the different gestational periods. The developed model is used to solve the case of exposure to overhead power transmission lines at different stages of pregnancy including weeks 8, 13, 26 and 38. The results obtained are in line with those published in the earlier works considering different approaches. In addition, a sensitivity analysis involving varying scenarios of conductivity, foetus postures and geometry for each stage is defined and solved. Finally, a correlation between the externally applied electric field and the current density inside the foetus is established and the zones of maximum exposure are identified.


2007 ◽  
Vol 135 (7) ◽  
pp. 2525-2544 ◽  
Author(s):  
Eric C. Bruning ◽  
W. David Rust ◽  
Terry J. Schuur ◽  
Donald R. MacGorman ◽  
Paul R. Krehbiel ◽  
...  

Abstract On 28–29 June 2004 a multicellular thunderstorm west of Oklahoma City, Oklahoma, was probed as part of the Thunderstorm Electrification and Lightning Experiment field program. This study makes use of radar observations from the Norman, Oklahoma, polarimetric Weather Surveillance Radar-1988 Doppler, three-dimensional lightning mapping data from the Oklahoma Lightning Mapping Array (LMA), and balloon-borne vector electric field meter (EFM) measurements. The storm had a low flash rate (30 flashes in 40 min). Four charge regions were inferred from a combination of LMA and EFM data. Lower positive charge near 4 km and midlevel negative charge from 4.5 to 6 km MSL (from 0° to −6.5°C) were generated in and adjacent to a vigorous updraft pulse. Further midlevel negative charge from 4.5 to 6 km MSL and upper positive charge from 6 to 8 km (from −6.5° to −19°C) were generated later in quantity sufficient to initiate lightning as the updraft decayed. A negative screening layer was present near the storm top (8.5 km MSL, −25°C). Initial lightning flashes were between lower positive and midlevel negative charge and started occurring shortly after a cell began lofting hydrometeors into the mixed phase region, where graupel was formed. A leader from the storm’s first flash avoided a region where polarimetric radar suggested wet growth and the resultant absence of noninductive charging of those hydrometeors. Initiation locations of later flashes that propagated into the upper positive charge tracked the descending location of a polarimetric signature of graupel. As the storm decayed, electric fields greater than 160 kV m−1 exceeded the minimum threshold for lightning initiation suggested by the hypothesized runaway breakdown process at 5.5 km MSL, but lightning did not occur. The small spatial extent (≈100 m) of the large electric field may not have been sufficient to allow runaway breakdown to fully develop and initiate lightning.


2014 ◽  
Vol 70 (a1) ◽  
pp. C674-C674
Author(s):  
Sajesh Thomas ◽  
Rebecca Fuller ◽  
Alexandre Sobolev ◽  
Philip Schauer ◽  
Simon Grabowsky ◽  
...  

The effect of an electric field on the vibrational spectra, the Vibrational Stark Effect (VSE), has been utilized extensively to probe the local electric field in the active sites of enzymes [1, 2]. For this reason, the electric field and consequent polarization effects induced by a supramolecular host system upon its guest molecules attain special interest due to the implications for various biological processes. Although the host-guest chemistry of crown ether complexes and clathrates is of fundamental importance in supramolecular chemistry, many of these multicomponent systems have yet to be explored in detail using modern techniques [3]. In this direction, the electrostatic features associated with the host-guest interactions in the inclusion complexes of halogenated acetonitriles and formamide with 18-crown-6 host molecules have been analyzed in terms of their experimental charge density distribution. The charge density models provide estimates of the molecular dipole moment enhancements which correlate with the simulated values of dipole moments under electric field. The accurate electron density mapping using the multipole formalism also enable the estimation of the electric field experienced by the guest molecules. The electric field vectors thus obtained were utilized to estimate the vibrational stark effect in the nitrile (-C≡N) and carbonyl (C=O) stretching frequencies of the guest molecules via quantum chemical calculations in gas phase. The results of these calculations indicate remarkable elongation of C≡N and C=O bonds due to the electric fields. The electronic polarization in these covalent bonds induced by the field manifests as notable red shifts in their characteristic vibrational frequencies. These results derived from the charge densities are further supported by FT-IR experiments and thus establish the significance of a phenomenon that could be termed as the "supramolecular Stark effect" in crystal environment.


2020 ◽  
Author(s):  
Matthew Hennefarth ◽  
Anastassia N. Alexandrova

<div> <div> <div> <p>External electric fields have proven to be an effective tool in catalysis, on par with pressure and temperature, affecting the thermodynamics and kinetics of a reaction. However, fields in molecules are complicated heterogeneous vector objects, and there is no universal recipe for grasping the exact features of these fields that implicate reactivity. Herein, we demonstrate that topological features of the heterogeneous electric field within the reactant state, as well as of the quantum mechanical electron density – a scalar reporter on the field experienced by the system – can be identified as rigorous descriptors of the reactivity to follow. We scrutinize specifically the Diels-Alder reaction. Its 3-D nature and the lack of a singular directionality of charge movement upon barrier crossing makes the effect of the electric field not obvious. We show that the electric field topology around the dienophile double bond, and the associated changes in the topology of the electron density in this bond are predictors of the reaction barrier. They are also the metrics by which to rationalize and predict how the external field would inhibit or enhance the reaction. The findings pave the way toward designing external fields for catalysis, as well as reading the reactivity without an explicit mechanistic interrogation, for a variety of reactions. </p> </div> </div> </div>


Author(s):  
Yin Ma ◽  
Tong Li ◽  
Jun Yan ◽  
Xiaorong Wang ◽  
Ji Gao ◽  
...  

Electric field assisted combustion is an important means to improve fuel combustion efficiency. This paper conducts extensive research on flame characteristics under different forms and different application methods of electric fields, emission of soot particles and simulation status. Different flame parameter measurement methods will lead to different degrees of error, and perfect numerical simulation can make simple predictions on experimental data. Most of the current numerical simulations are in two dimensions, and it is necessary to develop a complete and accurate three-dimensional model to simulate and predict the characteristics of the flame under an electric field. The emission of soot particles is also affected by the electric field, and reasonable electric field parameters can greatly reduce the emission of soot particles. It is recommended to conduct centralized measurement of different fuels under the electric field under high pressure and temperature conditions, so as to be able to develop a wider and more accurate flame dynamics and chemical model under the electric field.


2007 ◽  
Vol 17 (06) ◽  
pp. 845-876 ◽  
Author(s):  
PATRICK CIARLET ◽  
SAMIR KADDOURI

We are interested in computing the charge density and the electric field at the rounded tip of an electrode of small curvature. As a model, we focus on solving the electrostatic problem for the electric potential. For this problem, Peek's empirical formulas describe the relation between the electric field at the surface of the electrode and its curvature radius. However, it can be used only for electrodes with either a purely cylindrical, or a purely spherical, geometrical shape. Our aim is to justify rigorously these formulas, and to extend it to more general, two-dimensional, or three-dimensional axisymmetric, geometries. With the help of multiscaled asymptotic expansions, we establish an explicit formula for the electric potential in geometries that coincide with a cone at infinity. We also prove a formula for the surface charge density, which is very simple to compute with the Finite Element Method. In particular, the meshsize can be chosen independently of the curvature radius. We illustrate our mathematical results by numerical experiments.


1999 ◽  
Vol 384 ◽  
pp. 59-91 ◽  
Author(s):  
S. M. LEE ◽  
I. S. KANG

A three-dimensional analysis is performed to investigate the effects of an electric field on the steady deformation and small-amplitude oscillation of a bubble in dielectric liquid. To deal with a general class of electric fields, an electric field near the bubble is approximately represented by the sum of a uniform field and a linear field. Analytical results have been obtained for steady deformation and modification of oscillation frequency by using the domain perturbation method with the angular momentum operator approach.It has been found that, to the first order, the steady shape of a bubble in an arbitrary electric field can be represented by a linear combination of a finite number of spherical harmonics Yml, where 0[les ]l[les ]4 and [mid ]m[mid ][les ]l. For the oscillation about the deformed steady shape, the overall frequency modification from the value of free oscillation about a spherical shape is obtained by considering two contributions separately: (i) that due to the deformed steady shape (indirect effect), and (ii) that due to the direct effect of an electric field. Both the direct and indirect effects of an electric field split the (2l+1)-fold degenerate frequency of Yml modes, in the case of free oscillation about a spherical shape, into different frequencies that depend on m. However, when the average is taken over the (2l+1) values of m, the frequency splitting due to the indirect effect via the deformed steady shape preserves the average value, while the splitting due to the direct effect of an electric field does not.The oscillation characteristics of a bubble in a uniform electric field under the negligible compressibility assumption are compared with those of a conducting drop in a uniform electric field. For axisymmetric oscillation modes, deforming the steady shape into a prolate spheroid has the same effect of decreasing the oscillation frequency in both the drop and the bubble. However, the electric field has different effects on the oscillation about a spherical shape. The oscillation frequency increases with the increase of electric field in the case of a bubble, while it decreases in the case of a drop. This fundamental difference comes from the fact that the electric field outside the bubble exerts a suppressive surface force while the electric field outside the conducting drop exerts a pulling force on the surface.


2019 ◽  
Vol 89 (18) ◽  
pp. 3850-3859 ◽  
Author(s):  
Na Meng ◽  
Yuansheng Zheng ◽  
Binjie Xin

The electric field plays a key role in the formation of fibers during the electrospinning process. The electric field strength and shape caused by the applied voltage between the spinneret and collector govern the electrospinning process. In this study, a comprehensively designed and correctly implemented analysis was carried out to investigate the effects of the electric field on jet behavior and fiber morphology. Both working distance and applied voltage, respectively, were adjusted to manipulate the electric field shape and strength. The three-dimensional electric fields were simulated to understand the electric field distribution; in addition, a high-speed camera was adopted to capture the images of jet motion. Four parameters, namely straight jet length, envelope cone, height of the bending area, and velocity of the bending jet, were measured to describe the jet behavior. It can be revealed that the shape and strength of the electric field are responsible for the jet behavior and the fiber morphology, which include resultant ripples, grooves, and pores.


2019 ◽  
Vol 5 (6) ◽  
pp. eaaw3072 ◽  
Author(s):  
Xiaoyan Huang ◽  
Chun Tang ◽  
Jieqiong Li ◽  
Li-Chuan Chen ◽  
Jueting Zheng ◽  
...  

Oriented external electric fields (OEEFs) offer a unique chance to tune catalytic selectivity by orienting the alignment of the electric field along the axis of the activated bond for a specific chemical reaction; however, they remain a key experimental challenge. Here, we experimentally and theoretically investigated the OEEF-induced selective catalysis in a two-step cascade reaction of the Diels-Alder addition followed by an aromatization process. Characterized by the mechanically controllable break junction (MCBJ) technique in the nanogap and confirmed by nuclear magnetic resonance (NMR) in bottles, OEEFs are found to selectively catalyze the aromatization reaction by one order of magnitude owing to the alignment of the electric field on the reaction axis. Meanwhile, the Diels-Alder reaction remained unchanged since its reaction axis is orthogonal to the electric fields. This orientation-selective catalytic effect of OEEFs reveals that chemical reactions can be selectively manipulated through the elegant alignment between the electric fields and the reaction axis.


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