{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Wright D"],"funding":["Leverhulme Trust","European Research Council","Deutsche Akademie der Naturforscher Leopoldina - Nationale Akademie der Wissenschaften","UK Research and Innovation","Engineering and Physical Sciences Research Council"],"pagination":["4905-4911"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9189927"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["13(22)"],"pubmed_abstract":["Molecules containing vibrational Stark shift reporters provide a useful tool for measuring DC electric fields <i>in situ</i>. 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 molec"],"journal":["The journal of physical chemistry letters"],"pubmed_title":["Vibrational Stark Effects: Ionic Influence on Local Fields."],"pmcid":["PMC9189927"],"funding_grant_id":["ECF-2018-375","829067","883703","EP/L015978/1","MR/S015329/2","EP/L027151/1","861950"],"pubmed_authors":["Lin Q","Baumberg JJ","Sadeghi H","Sangtarash S","Wright D","Mueller NS"],"additional_accession":[]},"is_claimable":false,"name":"Vibrational Stark Effects: Ionic Influence on Local Fields.","description":"Molecules containing vibrational Stark shift reporters provide a useful tool for measuring DC electric fields <i>in situ</i>. 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 molec","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Jun","modification":"2025-04-05T15:33:59.457Z","creation":"2025-04-05T15:33:59.457Z"},"accession":"S-EPMC9189927","cross_references":{"pubmed":["35623089"],"doi":["10.1021/acs.jpclett.2c01048"]}}