Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-48413
Perakis, F; Hamm, P (2011). Two-dimensional infrared spectroscopy of supercooled water. Journal of Physical Chemistry. B, 115(18):5289-5293.
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We present two-dimensional infrared (2D IR) spectra of the OD stretch vibration of isotope diluted water (HOD/H2O) from ambient conditions (293 K) down to the metastable supercooled regime (260 K). We observe that spectral diffusion slows down from 700 fs to 2.6 ps as we lower the temperature. A comparison between measurements performed at the magic angle with those at parallel polarization shows that the 2D IR line shape is affected by the frequency-dependent anisotropy decay in the case of parallel polarization, altering the extracted correlation decay. A fit within the framework of an Arrhenius law reveals an activation energy of Ea = 6.2 ± 0.2 kcal/mol and a pre-exponential factor of 1/A = 0.02 ± 0.01 fs. Alternatively, a power law fit results in an exponent γ = 2.2 and a singularity temperature Ts = 221 K. We tentatively conclude that the power law provides the better physical picture to describe the dynamics of liquid water around the freezing point.
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|Item Type:||Journal Article, refereed, original work|
|Communities & Collections:||07 Faculty of Science > Department of Chemistry|
|Dewey Decimal Classification:||540 Chemistry|
|Deposited On:||09 Sep 2011 12:29|
|Last Modified:||05 Apr 2016 14:56|
|Publisher:||American Chemical Society|
|Funders:||Swiss National Science Foundation (SNF) trough NCCR MUST|
|Additional Information:||This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry. B, copyright © American Chemical Society after peer review and technical editing by the publisher.|
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