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Vibrational stark effects : ionic influence on local fields
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Wright, Demelza, Sangtarash, Sara, Mueller, Niclas S., Lin, Qianqi, Sadeghi, Hatef and Baumberg, Jeremy J. (2022) Vibrational stark effects : ionic influence on local fields. The Journal of Physical Chemistry Letters, 13 (22). pp. 4905-4911. doi:10.1021/acs.jpclett.2c01048 ISSN 1948-7185.
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Official URL: https://doi.org/10.1021/acs.jpclett.2c01048
Abstract
Molecules containing vibrational Stark shift reporters provide a useful tool for measuring DC electric fields in situ. To quantify this effect theoretically, density functional theory (DFT) calculations are usually utilized in a uniform electric field. However, using a combined theoretical and experimental study, we demonstrate here that uniform field DFT cannot simultaneously model the behavior of the three strongest vibrational modes in molecules forming a monolayer on an electrode. We show, by directly modeling ionic movement, that the measured Stark shifts are explained by partial electrical double-layer penetration into the molecular layer. This effect is sensitive to the local environment, and the Stark shifts can be fully suppressed experimentally by introducing a mixed molecular layer that prevents ionic double-layer penetration.
Item Type: | Journal Article | |||||||||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Engineering > Engineering | |||||||||||||||||||||||||||
SWORD Depositor: | Library Publications Router | |||||||||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Electrodes, Ions, Molecules, Infrared spectroscopy, Molecular spectroscopy, Vibrational spectra, Raman spectroscopy | |||||||||||||||||||||||||||
Journal or Publication Title: | The Journal of Physical Chemistry Letters | |||||||||||||||||||||||||||
Publisher: | American Chemical Society (ACS) | |||||||||||||||||||||||||||
ISSN: | 1948-7185 | |||||||||||||||||||||||||||
Official Date: | 9 June 2022 | |||||||||||||||||||||||||||
Dates: |
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Volume: | 13 | |||||||||||||||||||||||||||
Number: | 22 | |||||||||||||||||||||||||||
Page Range: | pp. 4905-4911 | |||||||||||||||||||||||||||
DOI: | 10.1021/acs.jpclett.2c01048 | |||||||||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||||||||
Date of first compliant deposit: | 11 July 2022 | |||||||||||||||||||||||||||
Date of first compliant Open Access: | 11 July 2022 | |||||||||||||||||||||||||||
RIOXX Funder/Project Grant: |
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