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Issue 39, 2011
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Polar solvation dynamics in water and methanol: search for molecularity

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Abstract

Time-dependent Stokes shifts (TDSS) were measured for diverse polarity probes in water, heavy water, methanol, and benzonitrile, by broadband fluorescence up-conversion with 85 fs time resolution. In water the spectral dynamics is solute-independent and quantitatively described by simple dielectric continuum theory of solvation. In methanol the slower part of the TDSS is solute-dependent. A correlation with anisotropy decay suggests that methanol solvation dynamics is modulated by orientational solute diffusion. An empirical power law which links the solvation relaxation function of a mobile solute to that of an immobile solute is experimentally verified. Activation energies for the average relaxation rate are also given. Solvation dynamics in H2O and D2O are identical at and above 20 °C but diverge below.

Graphical abstract: Polar solvation dynamics in water and methanol: search for molecularity

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Publication details

The article was received on 02 Jun 2011, accepted on 15 Aug 2011 and first published on 01 Sep 2011


Article type: Paper
DOI: 10.1039/C1CP21794A
Citation: Phys. Chem. Chem. Phys., 2011,13, 17768-17774
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    Polar solvation dynamics in water and methanol: search for molecularity

    M. Sajadi, M. Weinberger, H. Wagenknecht and N. P. Ernsting, Phys. Chem. Chem. Phys., 2011, 13, 17768
    DOI: 10.1039/C1CP21794A

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