Excited-state symmetry breaking is an ultrasensitive tool for probing microscopic electric fields

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dc.contributor.authorDereka, Bogdan
dc.contributor.authorMaroli, Nikhil
dc.contributor.authorPoronik, Yevgen M.
dc.contributor.authorGryko, Daniel T.
dc.contributor.authorKananenka, Alexei A.
dc.contributor.organizationDepartment of Chemistry, University of Zurich
dc.contributor.organizationDepartment of Physics and Astronomy, University of Delaware, USA
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciences
dc.date.accessioned2024-10-29T15:44:17Z
dc.date.available2024-10-29T15:44:17Z
dc.date.issued2024
dc.description.abstractMicroscopic electric fields are increasingly found to play a pivotal role in catalysis of enzymatic and chemical reactions. Currently, the vibrational Stark effect is the main experimental method used to measure them. Here, we demonstrate how excited-state symmetry breaking can serve as a much more sensitive tool to assess these fields. Using transient infrared spectroscopy on a quadrupolar probe equipped with nitrile groups we demonstrate both its superior sensitivity and that it does not suffer from the notorious hydrogen-bond induced upshift of the C[triple bond, length as m-dash]N stretch frequency. In combination with conventional ground-state infrared absorption, excited-state symmetry breaking can be used to disentangle even weak specific hydrogen bond interactions from general field effects. We showcase this capability with the example of weak C–H hydrogen bonds in polar aprotic solvents. Additionally, we reveal for the first time symmetry breaking driven not by solvent but by the entropy of the pendant side chains of the chromophore. Our findings not only enhance our understanding of symmetry-breaking charge-transfer phenomena but pave the way toward using them in electric field sensing modality.en
dc.description.sponsorshipSwiss National Science Foundation (grant PZ00P2_201996); National Science Center, Poland (grant OPUS 2020/37/B/ST4/00017).
dc.identifier.citationChem. Sci., 2024, 15, 15565–15576 ; https://doi.org/10.1039/D4SC04797D
dc.identifier.doi10.1039/D4SC04797D
dc.identifier.issn2041-6539
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/25012
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.rightsUznanie autorstwa 3.0 Unporteden
dc.rights.urihttp://creativecommons.org/licenses/by/3.0/
dc.sourceChemical Science
dc.titleExcited-state symmetry breaking is an ultrasensitive tool for probing microscopic electric fieldsen
dc.typearticle
dc.type.versionpublishedVersion
person.identifier.orcidPoronik, Yevgen M. [0000-0002-6744-2132]
person.identifier.orcidGryko, Daniel T. [0000-0002-2146-1282]
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