Electric Field Effect on Condensed-Phase Molecular Systems. IX. Control of Proton Displacement in Matrix-Isolated Hydrogen Chloride–Water Complexes

Park, Youngwook; Kang, Hani; Kang, Heon

doi:10.1021/acs.jpcc.9b09250

Cited by 6 publications

(10 citation statements)

References 36 publications

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“…A prototypical system is the monohydrated HCl complex, HCl–H 2 O, where HCl donates a hydrogen bond to the oxygen atom of H 2 O, isolated in the Ar matrix. The H–Cl bond length was elongated by about 0.4 pm from the equilibrium position upon the application of an external field parallel to the PT coordinate with an apparent strength of about 10 8 V/m, as inferred from the vibrational spectra of HCl (Figure a) and quantum calculations . The observed frequency shift of the HCl vibration associated with the elongation of H–Cl bond in the complex was about 29 cm –1 /(10 8 V/m), which is 1 order of magnitude larger than that of the uncomplexed HCl monomer, 2.7 cm –1 /(10 8 V/m) .…”

Section: Reaction: Proton Transfer Processesmentioning

confidence: 62%

“…(right) Molecular cartoon that illustrates the influence of parallel (red) and antiparallel (blue) electric fields that results in the elongation and contraction of the H–Cl distance, respectively. Reproduced with permission from ref . Copyright 2020 American Chemical Society.…”

Section: Reaction: Proton Transfer Processesmentioning

confidence: 99%

“…The proton dislocation along the PT coordinate of the HCl–H 2 O complex under the influence of 10 8 V/m external electrostatic field is highly asymmetric with respect to the elongation and contraction of the H–Cl bond. In the series of Stark spectra (Figure a), the Stark blue-shifting component changes about 4–5 times slower in frequency (6.5 cm –1 /(10 8 V/m)) than the red-shifting component (29 cm –1 /(10 8 V/m)), according to the analysis of vibrational Stark effect . A quantum calculation well simulates the experimental Stark spectra, with the parametric proton displacement of H–Cl bond elongation about 3–4 times larger than that of contraction at the apparent field strength of 10 8 V/m .…”

Section: Reaction: Proton Transfer Processesmentioning

confidence: 99%

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Recent Progress in the Manipulation of Molecules with DC Electric Fields

2020

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS:The structure and reactivity of a molecule in the condensed phase are governed by its intermolecular interactions with the surrounding environment. The multipole expansion of each molecule in the condensed phase indicates that the intermolecular interactions are essentially electrostatic (e.g., ion−dipole, dipole− dipole, dipole−quadrupole, dipole−induced dipole). The electrostatic field is a fundamental language of intermolecular communications. Therefore, understanding the influence of the electrostatic field on a molecule, that is, the mechanisms by which an electrostatic field manipulates a molecule, from the perspective of molecular structure, energy states, and dynamics is indispensable for illustrating and, by extension, controlling the chemistry in molecular systems.In this Account, we describe the recent progress made in manipulation of molecular processes using an external DC electrostatic field. An electrostatic field with unprecedentedly high strength (≤4 × 10 8 V/m) was applied in a controlled manner across a molecular film sample using the ice film nanocapacitor method. This field strength is comparable in magnitude to that of weak intermolecular interactions such as van der Waals interactions in the condensed phases. The samples were prepared using a thin film growing technique in vacuum to obtain the desired chemically tailored molecular systems. The examples of prepared systems included small molecules and molecular clusters isolated in cryogenic Ar matrices, frozen molecular films in amorphous or crystalline phase, and interfaces of multilayered molecular films. The response of the molecules to the external field was monitored by reflection−absorption infrared spectroscopy. This approach allowed us to investigate a variety of molecular systems with various intermolecular strength and environments under the influence of strong electrostatic fields. The range of observed molecular behaviors includes the manipulation of molecular orientation, intramolecular dynamics, and proton transfer reactions as an example of stereodynamic control of chemical reactivity. These observations improve our understanding of molecular behaviors in strong electric fields and broaden our perspective on electrostatic manipulation of molecules. This information is also relevant to a variety of research topics in physical and biological sciences where electric fields play a role in molecular and biological functions.

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Section: Reaction: Proton Transfer Processesmentioning

confidence: 62%

Section: Reaction: Proton Transfer Processesmentioning

confidence: 99%

Section: Reaction: Proton Transfer Processesmentioning

confidence: 99%

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Recent Progress in the Manipulation of Molecules with DC Electric Fields

2020

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“…Proton conductivities along proton chains were also found to be greater than in the perpendicular direction [95]. Finally, since the field-induced proton displacement is tiny (on the order of 10 -3 to 10 -4 Å for short hydrogen bonds for applied fields under 1 MV/cm, Section S8, see also [96]) compared to the proton-chromophore distance (on the order of Å), proton polarization can indeed be well approximated as a point dipole.…”

Section: S7 Local Field Factor ƒHb Due To Proton Polarizability Of Shmentioning

confidence: 88%

Unusual Spectroscopic and Electric Field Sensitivity of Chromophores with Short Hydrogen Bonds: GFP and PYP as Model Systems

Lin

Boxer

2020

J. Phys. Chem. B

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Short hydrogen bonds, with heavy-atom distances less than 2.7 Å, are believed to exhibit proton delocalization and their possible role in catalysis has been widely debated. While spectroscopic and/or structural methods are usually employed to study the degree of proton delocalization, ambiguities still arise and no direct information on the corresponding potential energy surface is obtained. Here we apply an external electric field to perturb the short hydrogen bond(s) within a collection of green fluorescent protein S65T/H148D variants and photoactive yellow protein mutants, where the chromophore participates in the short hydrogen bond(s) and serves as an optical probe of the proton position. As the proton is charged, its position may shift in response to the external electric field, and the chromophore's electronic absorption can thus reflect the ease of proton transfer. The results suggest that low-barrier hydrogen bonds are not present within these proteins even when proton affinities between donor and acceptor are closely matched. Exploiting the chromophores as pre-calibrated electrostatic probes, the covalency of short hydrogen bonds as a non-electrostatic component was also revealed. No clear evidence was found for a possible contribution of unusually large polarizabilities of short hydrogen bonds due to proton delocalization; a theoretical framework for this interesting phenomenon is developed.

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“…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.…”

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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Electric Field Effect on Condensed-Phase Molecular Systems. IX. Control of Proton Displacement in Matrix-Isolated Hydrogen Chloride–Water Complexes

Cited by 6 publications

References 36 publications

Recent Progress in the Manipulation of Molecules with DC Electric Fields

Recent Progress in the Manipulation of Molecules with DC Electric Fields

Unusual Spectroscopic and Electric Field Sensitivity of Chromophores with Short Hydrogen Bonds: GFP and PYP as Model Systems

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

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Electric Field Effect on Condensed-Phase Molecular Systems. IX. Control of Proton Displacement in Matrix-Isolated Hydrogen Chloride–Water Complexes

Cited by 6 publications

References 36 publications

Recent Progress in the Manipulation of Molecules with DC Electric Fields

Recent Progress in the Manipulation of Molecules with DC Electric Fields

Unusual Spectroscopic and Electric Field Sensitivity of Chromophores with Short Hydrogen Bonds: GFP and PYP as Model Systems

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

Contact Info

Product

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