Cargando…
Inhomogeneity of Interfacial Electric Fields at Vibrational Probes on Electrode Surfaces
[Image: see text] Electric fields control chemical reactivity in a wide range of systems, including enzymes and electrochemical interfaces. Characterizing the electric fields at electrode–solution interfaces is critical for understanding heterogeneous catalysis and associated energy conversion proce...
Autores principales: | , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2020
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7047426/ https://www.ncbi.nlm.nih.gov/pubmed/32123749 http://dx.doi.org/10.1021/acscentsci.9b01297 |
_version_ | 1783502139407990784 |
---|---|
author | Goldsmith, Zachary K. Secor, Maxim Hammes-Schiffer, Sharon |
author_facet | Goldsmith, Zachary K. Secor, Maxim Hammes-Schiffer, Sharon |
author_sort | Goldsmith, Zachary K. |
collection | PubMed |
description | [Image: see text] Electric fields control chemical reactivity in a wide range of systems, including enzymes and electrochemical interfaces. Characterizing the electric fields at electrode–solution interfaces is critical for understanding heterogeneous catalysis and associated energy conversion processes. To address this challenge, recent experiments have probed the response of the nitrile stretching frequency of 4-mercaptobenzonitrile (4-MBN) attached to a gold electrode to changes in the solvent and applied electrode potential. Herein, this system is modeled with periodic density functional theory using a multilayer dielectric continuum treatment of the solvent and at constant applied potentials. The impact of the solvent dielectric constant and the applied electrode potential on the nitrile stretching frequency computed with a grid-based method is in qualitative agreement with the experimental data. In addition, the interfacial electrostatic potentials and electric fields as a function of applied potential were calculated directly with density functional theory. Substantial spatial inhomogeneity of the interfacial electric fields was observed, including oscillations in the region of the molecular probe attached to the electrode. These simulations highlight the microscopic inhomogeneity of the electric fields and the role of molecular polarizability at electrode–solution interfaces, thereby demonstrating the limitations of mean-field models and providing insights relevant to the interpretation of vibrational Stark effect experiments. |
format | Online Article Text |
id | pubmed-7047426 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-70474262020-03-02 Inhomogeneity of Interfacial Electric Fields at Vibrational Probes on Electrode Surfaces Goldsmith, Zachary K. Secor, Maxim Hammes-Schiffer, Sharon ACS Cent Sci [Image: see text] Electric fields control chemical reactivity in a wide range of systems, including enzymes and electrochemical interfaces. Characterizing the electric fields at electrode–solution interfaces is critical for understanding heterogeneous catalysis and associated energy conversion processes. To address this challenge, recent experiments have probed the response of the nitrile stretching frequency of 4-mercaptobenzonitrile (4-MBN) attached to a gold electrode to changes in the solvent and applied electrode potential. Herein, this system is modeled with periodic density functional theory using a multilayer dielectric continuum treatment of the solvent and at constant applied potentials. The impact of the solvent dielectric constant and the applied electrode potential on the nitrile stretching frequency computed with a grid-based method is in qualitative agreement with the experimental data. In addition, the interfacial electrostatic potentials and electric fields as a function of applied potential were calculated directly with density functional theory. Substantial spatial inhomogeneity of the interfacial electric fields was observed, including oscillations in the region of the molecular probe attached to the electrode. These simulations highlight the microscopic inhomogeneity of the electric fields and the role of molecular polarizability at electrode–solution interfaces, thereby demonstrating the limitations of mean-field models and providing insights relevant to the interpretation of vibrational Stark effect experiments. American Chemical Society 2020-02-03 2020-02-26 /pmc/articles/PMC7047426/ /pubmed/32123749 http://dx.doi.org/10.1021/acscentsci.9b01297 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Goldsmith, Zachary K. Secor, Maxim Hammes-Schiffer, Sharon Inhomogeneity of Interfacial Electric Fields at Vibrational Probes on Electrode Surfaces |
title | Inhomogeneity of Interfacial Electric Fields at Vibrational
Probes on Electrode Surfaces |
title_full | Inhomogeneity of Interfacial Electric Fields at Vibrational
Probes on Electrode Surfaces |
title_fullStr | Inhomogeneity of Interfacial Electric Fields at Vibrational
Probes on Electrode Surfaces |
title_full_unstemmed | Inhomogeneity of Interfacial Electric Fields at Vibrational
Probes on Electrode Surfaces |
title_short | Inhomogeneity of Interfacial Electric Fields at Vibrational
Probes on Electrode Surfaces |
title_sort | inhomogeneity of interfacial electric fields at vibrational
probes on electrode surfaces |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7047426/ https://www.ncbi.nlm.nih.gov/pubmed/32123749 http://dx.doi.org/10.1021/acscentsci.9b01297 |
work_keys_str_mv | AT goldsmithzacharyk inhomogeneityofinterfacialelectricfieldsatvibrationalprobesonelectrodesurfaces AT secormaxim inhomogeneityofinterfacialelectricfieldsatvibrationalprobesonelectrodesurfaces AT hammesschiffersharon inhomogeneityofinterfacialelectricfieldsatvibrationalprobesonelectrodesurfaces |