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Vibrational Stark Effects: Ionic Influence on Local Fields.

Accepted version
Peer-reviewed

Type

Article

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Authors

Sangtarash, Sara 
Lin, Qianqi 

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.

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Keywords

Journal Title

J Phys Chem Lett

Conference Name

Journal ISSN

1948-7185
1948-7185

Volume Title

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/L027151/1)
European Commission Horizon 2020 (H2020) Future and Emerging Technologies (FET) (829067)
European Commission Horizon 2020 (H2020) Research Infrastructures (RI) (861950)
European Commission Horizon 2020 (H2020) ERC (883703)
Engineering and Physical Sciences Research Council (EP/L015978/1)
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