The destabilization of hydrogen bonds in an external E‐field for improved switch performance

Xu, Ting; Momen, Roya; Azizi, Alireza; Mourik, Tanja van; Früchtl, Herbert; Kirk, Steven R.; Jenkins, Samantha

doi:10.1002/jcc.25843

Cited by 17 publications

(21 citation statements)

References 49 publications

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“…Previously we examined the directional character of the functioning of a recently proposed Fe‐doped switch involving hydrogen atom transfer in response to a varying E ‐field . This switching process involved the formation and breaking of chemical bonds.…”

Section: Introductionmentioning

confidence: 99%

“…Previously we examined the directional character of the functioning of a recently proposed Fe-doped switch [12] involving hydrogen atom transfer [13] in response to a varying E-field. [14] This switching process involved the formation and breaking of chemical bonds. More subtle than the details of the formation and rupture of chemical bonds [15][16][17][18][19] are changes to the electronic charge density distribution such as bond critical points (BCPs).…”

Section: Introductionmentioning

confidence: 99%

“…[26] This directional approach can be used in a variety of circumstances where conventional QTAIM, [27] that only provides scalar measures such as bond ellipticity ε, is not useful. Examples that highlight the utility of this directional approach of next-generation QTAIM include understanding the consequences of application of external forces, for example, normal modes [26] excited states, torsions, [14,28,29] and stereochemistry. [30] Theory and methods…”

Section: Introductionmentioning

confidence: 99%

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Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices

et al. 2019

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The effect of a varying, directional E x, E y, and E z electric field on the ethene molecule was investigated using next‐generation quantum theory of atoms in molecules (QTAIM). Despite using low E‐field strengths that are within the realm of experiment and do not measurably alter the molecular geometry, significant changes to the QTAIM properties were observed. Using conventional QTAIM, the shifting of the C─C and C─H bond critical points (BCPs) demonstrates polarization through an interchange in the size of the atoms involved in a bond, since a BCP is located on the boundary between a pair of bonded atoms. Next‐generation QTAIM, however, demonstrates the polarization effect more directly with a change in morphology of the 3‐D envelope around the BCP. Modest increases of ≈ 2% in the ellipticity ε of the BCP were uncovered when the C─C bond was aligned parallel or anti‐parallel to the applied E x‐field. Significant asymmetries were found in the response of the next‐generation QTAIM 3‐D paths of the C─H bonds to the applied E‐field. When the E‐field coincided with the C─C bond, the BCP moved in response and was accompanied by the envelope constructed from 3‐D next‐generation paths. The response displayed a polarization effect that increased with increasing magnitude of the E x‐field parallel and anti‐parallel to the C─C bond. Our analysis demonstrates that next‐generation QTAIM is a useful tool for understanding the response of molecules to E‐fields, for example, for the screening of molecular wires for the design of molecular electronic devices. © 2019 Wiley Periodicals, Inc.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices

et al. 2019

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“…]dr )} in sequence, forming the T σ (s ), constructed from the vector dot products (the dot product is a projection, or a measure of vectors being parallel to each other) of the stress tensor T σ (s ) eigenvector components evaluated at theBCP. The projections of dr are respectively associated with the bond torsion: e 1σ .dr -bond-twist, e 2σ .drbond-flexing ande 3σ .drbond-anharmonicity [30], [53]- [55], [57]- [59].…”

Section: Theoretical Background and Computational Detailsmentioning

confidence: 99%

Control of Chirality, Bond flexing and Anharmonicity in an Electric Field

Nie

et al. 2021

Preprint

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We located ‘hidden’ S-character chirality in formally achiral glycine using a vector-based interpretation of the total electronic charge density distribution. We induced the formation of stereoisomers in glycine by the application of an electric field. Control of chirality was indicated from the proportionate response to a non-structurally distorting electric field. The bond-flexing was determined to be a measure of bond strain, which could be a factor of three lower or higher, depending on the direction of the electric field, than in the absence of the electric field. The bond-anharmonicity was found to be approximately independent of the electric field. We also compared the formally achiral glycine with the chiral molecules alanine and lactic acid, quantifying the preferences for the S and R stereoisomers. The proportional response of the chiral discrimination to the magnitude and direction of the applied electric field indicated use of the chirality discrimination as a molecular similarity measure.

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“…Using the same idea, research is increasingly focused on regulating the stability of the reactants and transition states, as well as products, using artificial external electric fields through dipole‐field interaction, thereby manipulating the chemical reaction process. [ 17–44 ]…”

Section: Introductionmentioning

confidence: 99%

Oriented external electric fields regulating the oxidation reaction of CH₄ catalyzed by Mn‐corrolazine

Wang

Zheng

et al. 2020

Int J of Quantum Chemistry

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Mn-corrolazine-catalyzed CH 4 oxidation, as well as the regulation of its oriented external electric fields (OEEFs), is systematically studied using the first-principle calculations. Extensive density functional calculations show that the activation energy of CH 4 oxidation catalyzed by Mn-corrolazine is up to 38.5 kcal/mol in the field-free condition. However, when the OEEF is applied, the reactant and the transition state of the oxidation reaction are stabilized, originating from an attractive interaction between the increased dipole moment and the applied fields. Furthermore, when the field is negative, the activation energy decreases as the field increases. Especially for the negative field along the intrinsic Mn O reaction axis perpendicular to the corrolazine ring, of which the orientation is easily aligned in practical applications, when its intensity reaches −0.015 a.u., the activation energy of CH 4 oxidation is reduced to 25.0 kcal/mol. K E Y W O R D S catalysis, CH 4 oxidation, density functional theory calculations, Mn-corrolazine, oriented external electric field 1 | INTRODUCTION Searching for novel and efficient catalysts has always been the most important subject in chemical research. Traditionally, the common catalysts are molecules and the surfaces or interface in homogeneous and heterogeneous systems, [1-6] respectively. However, in recent years, many new technologies, such as ultrasound, [7] microwaves, [8] mechanical stress, [9] and nanoreactors, [10] have been used to control various reaction processes as novel catalysts. Electrostatic forces play an extremely important role in chemical reactions involving the arrangement of nuclei and electrons. [11-13] A typical example is the electrostatic catalysis of enzymes in nature. [10,14-16] The polar environment originating from the subtle arrangement of atoms around the active site produces the electric field that can efficiently and selectively catalyze various biochemical reactions. Using the same idea, research is increasingly focused on regulating the stability of the reactants and transition states, as well as products, using artificial external electric fields through dipole-field interaction, thereby manipulating the chemical reaction process. [17-44] Very recently, Shaik et al. performed a much computational research to explore the effect of oriented external electric fields (OEEFs) on organic reactions. [17-23] Their research results show that OFFEs along the reaction axis involving the electron transfer can significantly catalyze the organic reactions, while the OFFEs along other directions can control the regioselectivity and stereoselectivity, and some results are confirmed by experimental evidence provided by Aragonès et al. [18] However, although great progress has been made in both the experimental and theoretical research, [17-24,27,30] a major problem in using the OFFEs to manipulate reaction processes is to deliver the external electric fields and orient the molecules within the applied fields simultaneously. The corrole, a porph...

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The destabilization of hydrogen bonds in an external E‐field for improved switch performance

Cited by 17 publications

References 49 publications

Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices

Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices

Control of Chirality, Bond flexing and Anharmonicity in an Electric Field

Oriented external electric fields regulating the oxidation reaction of CH₄ catalyzed by Mn‐corrolazine

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The destabilization of hydrogen bonds in an external E‐field for improved switch performance

Cited by 17 publications

References 49 publications

Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices

Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices

Control of Chirality, Bond flexing and Anharmonicity in an Electric Field

Oriented external electric fields regulating the oxidation reaction of CH4 catalyzed by Mn‐corrolazine

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Product

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Oriented external electric fields regulating the oxidation reaction of CH₄ catalyzed by Mn‐corrolazine