Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

Kirshenboim, Omer; Frenklah, Alexander; Kozuch, Sebastian

doi:10.1039/d0sc06295b

Cited by 28 publications

(29 citation statements)

References 88 publications

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“…Works on catalysis have appeared, in which, instead of a material catalyst, the influence of an external electric field on the acceleration of chemical reactions is studied [15][16]. In them, the acceleration of the reaction occurs without a catalyst only under the action of an electric field.…”

Section: External Electromagnetic Field and Electrons As A Catalystmentioning

confidence: 99%

“…Recent studies have revealed a new type of physical influence on chemical reactions with the help of an external electric field, which is considered as a physical catalyst or pseudocatalyst [15,24]. But since the field is not a reactant, not a product and not even a substance [15], the IUPAC formulation is also not a universal definition of a catalyst. The field, as a catalyst or pseudocatalyst, is outside the scope of this IUPAC definition.…”

Section: Catalysts -Carriers (Generators) Of the Active Factor Of Cat...mentioning

confidence: 99%

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Laws of Heterogeneous Catalysis

Kaplunenko¹,

Kosinov²

2022

InterConf+

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Based on the generalization of experimental and theoretical studies in the field of catalysis, three basic laws of heterogeneous catalysis were discovered. From the formula of the catalysis rate law, the most important characteristics of catalysis are obtained - the reaction output, TOF and TON. Formulas for calculating the characteristics of catalysis using the characteristics of catalyst substance are given. A new concept of heterogeneous catalysis has been developed, in which the role of catalysts in the mechanism of accelerating chemical reactions has been revised. The oxidation states of the reactants and active sites of the catalyst are used as parameters in the formulas of the laws of catalysis. It follows from the laws of catalysis that oxidation states are such important characteristics of catalyst substance and reagents, that they directly affect the mechanism of catalysis itself and set the values of the most important characteristics of catalysis. As the main tool in the selection of catalysts, it is necessary to use the list of oxidation states of chemical elements known in chemistry. Based on the laws of catalysis, new definitions of catalyst and catalysis are given. The class of catalysts is expanded. Material catalysts are complemented by field catalysts. The substantiation of catalysis as a fundamental direction in science is given.

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Section: External Electromagnetic Field and Electrons As A Catalystmentioning

confidence: 99%

Section: Catalysts -Carriers (Generators) Of the Active Factor Of Cat...mentioning

confidence: 99%

Laws of Heterogeneous Catalysis

Kaplunenko¹,

Kosinov²

2022

InterConf+

View full text Add to dashboard Cite

show abstract

“…Since the field-induced change on regioselectivity in Diels–Alder (DA) reactions predicted by Shaik and co-workers was experimentally validated, this chemistry is becoming more tangible and there has been a reborn of the topic also from the theoretical perspective . Additionally, examples of the application of EEF on very diverse topics as the tuning of photo- and excited-state chemistry, switch molecular diodes, quantum tunneling, and homo- and heterogeneous catalysis have been successfully investigated. , …”

Section: Introductionmentioning

confidence: 99%

Fast and Simple Evaluation of the Catalysis and Selectivity Induced by External Electric Fields

et al. 2021

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In the oriented external electric-field-driven catalysis, the reaction rates and the selectivity of chemical reactions can be tuned at will. The activation barriers of chemical reactions within external electric fields of several strengths and directions can be computationally modeled. However, the calculation of all of the required field-dependent transition states and reactants is computationally demanding, especially for large systems. Herein, we present a method based on the Taylor expansion of the field-dependent energy of the reactants and transition states in terms of their field-free dipole moments and electrical (hyper)polarizabilities. This approach, called field-dependent energy barrier (FDB β ), allows systematic onedimensional (1D), two-dimensional (2D), and three-dimensional (3D) representations of the activation energy barriers for any strength and direction of the external electric field. The calculation of the field-dependent FDB β energy barriers has a computational cost several orders of magnitude lower than the explicit electric field optimizations, and the errors of the FDB β barriers are within the range of only 1−2 kcal•mol −1 . The achieved accuracy is sufficient for a fast-screening tool to study and predict potential electric-fieldinduced catalysis, regioselectivity, and stereoselectivity. As illustrative examples, four cycloadditions (1,3-dipolar and Diels−Alder) are studied.

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“…10−12 Using an external field, the rate of the ultracold chemical reactions could be tuned by varying the field strength. 13 The use of oriented external electric fields has opened new scientific possibilities such as the controlled modulation of molecular reactivity 14,15 and selective catalysis of single-molecule reactions. 16 Here, we demonstrate that it is possible to manipulate the molecular aggregation process of polar molecules at ultracold temperatures just by using an internal electric field created by a single molecular dipole, e.g., HCl.…”

mentioning

confidence: 99%

“…The strong external static electric field allows laser-induced one-dimensional alignment of state-selected polar molecules, offering new opportunities in molecular science. − Using an external field, the rate of the ultracold chemical reactions could be tuned by varying the field strength . The use of oriented external electric fields has opened new scientific possibilities such as the controlled modulation of molecular reactivity , and selective catalysis of single-molecule reactions …”

mentioning

confidence: 99%

Internal Electric Field-Induced Formation of Exotic Linear Acetonitrile Chains

Mani

Roy

Khatri

et al. 2022

J. Phys. Chem. Lett.

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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.

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Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

Abstract: Adding an external electric field to reactions driven by quantum mechanical tunneling brings a whole new dimension to the idea of switch chemistry.

Cited by 28 publications

References 88 publications

Laws of Heterogeneous Catalysis

Laws of Heterogeneous Catalysis

Fast and Simple Evaluation of the Catalysis and Selectivity Induced by External Electric Fields

Internal Electric Field-Induced Formation of Exotic Linear Acetonitrile Chains

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