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Time-resolved photodetachment anisotropy : gas-phase rotational and vibrational dynamics of the fluorescein anion.

Horke, D. A. and Chatterley, A. S. and Bull, J. N. and Verlet, J. R. R. (2015) 'Time-resolved photodetachment anisotropy : gas-phase rotational and vibrational dynamics of the fluorescein anion.', Journal of physical chemistry letters., 6 (1). pp. 189-194.


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.

Item Type:Article
Keywords:Gas-phase anions, Ultrafast dynamics, Electron detachment, Anisotropy, Photoelectron spectroscopy, Fluorescein, Wavepacket dynamics, Rotational anisotropy.
Full text:(AM) Accepted Manuscript
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Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © 2014 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Date accepted:No date available
Date deposited:25 February 2015
Date of first online publication:January 2015
Date first made open access:No date available

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