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

ABSTRACT: Microscopic 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 fiel

SUBMITTER: Dereka B 

PROVIDER: S-EPMC11350400 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature