Reactive dynamics in confined liquids: Ultrafast torsional dynamics of auramine O in nanoconfined water in aerosol OT reverse micelles

Heisler, Ismael, Kondo, Minako and Meech, Steve ORCID: https://orcid.org/0000-0001-5561-2782 (2009) Reactive dynamics in confined liquids: Ultrafast torsional dynamics of auramine O in nanoconfined water in aerosol OT reverse micelles. The Journal of Physical Chemistry B, 113 (6). pp. 1623-1631. ISSN 1520-5207

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Abstract

The effects of confinement on the ultrafast torsional reaction of auramine O in aqueous solution are investigated through ultrafast fluorescence up-conversion with 50 fs time resolution. The aqueous solution is confined in nanoscale water droplets by an ionic surfactant. The torsional motion is orders of magnitude slower in the confined droplets than in bulk aqueous solution. The dynamics become faster with increasing radius of the nanodroplet but never reach the bulk value, even when the radius is as large as 10 nm. Time-dependent fluorescence spectra were constructed and subsequently analyzed using a one-dimensional generalized Smoluchowski equation. An accurate description of the data was achieved using a time-dependent diffusion coefficient. This is suggested to arise because the medium friction reflects dynamics on a broad range of time scales spanning the reaction dynamics. The friction recovered suggests strongly hindered motion in the confined droplet and can be qualitatively related to solvation dynamics measured in AOT, consistent with auramine O torsional dynamics being accompanied by intramolecular charge redistribution.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017)
Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User: Rachel Smith
Date Deposited: 23 Mar 2011 13:04
Last Modified: 20 Aug 2023 00:14
URI: https://ueaeprints.uea.ac.uk/id/eprint/27007
DOI: 10.1021/jp808989f

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