Ultrafast Vibrational Stark-Effect Spectroscopy: Exploring Charge-Transfer Reactions by Directly Monitoring the Solvation Shell Response

作者：Baiz Carlos R; Kubarych Kevin J^*

来源：Journal of the American Chemical Society, 2010, 132(37): 12784-12785.

DOI：10.1021/ja1043853

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.

• 出版日期2010-9-22