Vibrational Stark Effects: Ionic Influence on Local Fields.
| cam.depositDate | 2022-05-24 | |
| cam.issuedOnline | 2022-05-27 | |
| cam.orpheus.counter | 2 | |
| cam.orpheus.success | Mon Jun 13 08:08:18 BST 2022 - Embargo updated | |
| datacite.issupplementedby.url | https://doi.org/10.17863/CAM.84952 | |
| dc.contributor.author | Wright, Demelza | |
| dc.contributor.author | Sangtarash, Sara | |
| dc.contributor.author | Mueller, Niclas S | |
| dc.contributor.author | Lin, Qianqi | |
| dc.contributor.author | Sadeghi, Hatef | |
| dc.contributor.author | Baumberg, Jeremy | |
| dc.contributor.orcid | Wright, Demelza [0000-0002-8854-2714] | |
| dc.contributor.orcid | Mueller, Niclas S [0000-0002-8688-1974] | |
| dc.contributor.orcid | Sadeghi, Hatef [0000-0001-5398-8620] | |
| dc.contributor.orcid | Baumberg, Jeremy [0000-0002-9606-9488] | |
| dc.date.accessioned | 2022-05-24T23:30:25Z | |
| dc.date.available | 2022-05-24T23:30:25Z | |
| dc.date.issued | 2022-06-09 | |
| dc.date.updated | 2022-05-24T10:59:21Z | |
| dc.description.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. | |
| dc.identifier.doi | 10.17863/CAM.84854 | |
| dc.identifier.eissn | 1948-7185 | |
| dc.identifier.issn | 1948-7185 | |
| dc.identifier.uri | https://www.repository.cam.ac.uk/handle/1810/337441 | |
| dc.language.iso | eng | |
| dc.publisher | American Chemical Society (ACS) | |
| dc.publisher.department | Department of Physics | |
| dc.rights | All Rights Reserved | |
| dc.rights.uri | http://www.rioxx.net/licenses/all-rights-reserved | |
| dc.title | Vibrational Stark Effects: Ionic Influence on Local Fields. | |
| dc.type | Article | |
| dcterms.dateAccepted | 2022-05-24 | |
| prism.publicationName | J Phys Chem Lett | |
| pubs.funder-project-id | Engineering and Physical Sciences Research Council (EP/L027151/1) | |
| pubs.funder-project-id | European Commission Horizon 2020 (H2020) Future and Emerging Technologies (FET) (829067) | |
| pubs.funder-project-id | European Commission Horizon 2020 (H2020) Research Infrastructures (RI) (861950) | |
| pubs.funder-project-id | European Commission Horizon 2020 (H2020) ERC (883703) | |
| pubs.funder-project-id | Engineering and Physical Sciences Research Council (EP/L015978/1) | |
| pubs.licence-display-name | Apollo Repository Deposit Licence Agreement | |
| pubs.licence-identifier | apollo-deposit-licence-2-1 | |
| rioxxterms.type | Journal Article/Review | |
| rioxxterms.version | AM | |
| rioxxterms.versionofrecord | 10.1021/acs.jpclett.2c01048 |
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