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Updated: Jun 9, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Ultrafast vibrational Stark-effect spectroscopy: exploring charge-transfer reactions by directly monitoring the
Carlos R Baiz1, Kevin J Kubarych
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 40109, USA.
Abstract:
We present the first implementation of transient vibrational Stark-effect spectroscopy as an ultrafast probe of solvation dynamics. The method is applied to the phototriggered intramolecular charge-transfer reaction of Betaine-30, where the vibrational Stark shifts of the nearby solvent molecules--arising from the change in the electrostatic environment--are measured using a three-pulse photon echo probe. This new experiment provides a direct subpicosecond measure of the chromophore's excited-state dynamics and back electron transfer as viewed from the solvent's perspective. We develop a simple ab initio model that offers semiquantitative prediction of the experimental Stark shifts.
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