Time-Resolved Photodetachment Anisotropy: Gas-Phase Rotational and Vibrational Dynamics of the Fluorescein Anion

Horke, D.A.; Chatterley, A.S.; Bull, J.N.; Verlet, J.R.R.

Abstract

The photoelectron signal of the singly deprotonated fluorescein anion is found to be highly dependent on the relative polarization between pump and probe pulses, and time-resolved photodetachment anisotropy (TR-PA) is developed as a probe of the rotational dynamics of the chromophore. The total photoelectron signal shows both rotational and vibrational wavepacket dynamics, and we demonstrate how TR-PA can readily disentangle these dynamical processes. TR-PA in fluorescein presents specific opportunities for its development as a probe for rotational dynamics in large biomolecules as fluorescein derivatives are commonly incorporated in complex biomolecules and have been used extensively in time-resolved fluorescence anisotropy measurements, to which TR-PA is a gas-phase analogue.

Citation

Horke, D., Chatterley, A., Bull, J., & Verlet, J. (2015). Time-Resolved Photodetachment Anisotropy: Gas-Phase Rotational and Vibrational Dynamics of the Fluorescein Anion. Journal of Physical Chemistry Letters, 6(1), 189-194. https://doi.org/10.1021/jz5022526

• Journal Article Type: Article
• Publication Date: Jan 2, 2015
• Deposit Date: Feb 18, 2015
• Publicly Available Date: Feb 25, 2015
• Journal: Journal of Physical Chemistry Letters
• Electronic ISSN: 1948-7185
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 6
• Issue: 1
• Pages: 189-194
• DOI: https://doi.org/10.1021/jz5022526
• Keywords: Gas-phase anions, Ultrafast dynamics, Electron detachment, Anisotropy, Photoelectron spectroscopy, Fluorescein, Wavepacket dynamics, Rotational anisotropy.
• Public URL: https://durham-repository.worktribe.com/output/1436576